Herbicides

ABSTRACT

Compounds of formula 
                 
 
wherein the substituents have the meanings given in claim 1, and agronomically tolerable salts, isomers and enantiomer of those compounds, are suitable for use as herbicides.

This application is a 371 of PCT/EP00/08656, filed Sep. 5, 2000.

The present invention relates to novel herbicidally active heterocycles substituted by a phenyl group, to processes for the preparation thereof, to compositions comprising such compounds, and to the use thereof in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.

3-Hydroxy-4-aryl-5-oxo-pyrazoline derivatives having herbicidal action are described, for example, in EP-A-0 508 126, WO 96/25395 and WO 96/21652.

Novel heterocycles substituted by a phenyl group having herbicidal and growth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

wherein

-   R₁ and R₃ are each independently of the other ethyl, haloethyl,     ethynyl, C₁-C₂alkoxy, C₁-C₂haloalkoxy, C₁-C₂alkylcarbonyl,     C₁-C₂hydroxyalkyl or C₁-C₂alkoxycarbonyl; -   Q is a group -   R₄ and R₅ are each independently of the other C₁-C₁₀alkyl,     C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl,     C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl,     C₂-C₁₀alkylcarbonylalkyl, C₂-C₁₀-N-alkoxyiminoalkyl,     C₂-C₁₀alkoxycarbonylalkyl, C₁-C₁₀aminoalkyl,     C₃-C₁₀dialkylaminoalkyl, C₂-C₁₀alkylaminoalkyl, C₁-C₁₀cyanoalkyl,     C₄-C₁₀cycloalkylalkyl, C₁-C₁₀phenylalkyl, C₁-C₁₀heteroarylalkyl,     C₁-C₁₀phenoxyalkyl, C₁-C₁₀heteroaryloxyalkyl,     C₁-C₁₀alkylideneaminooxyalkyl, C₁-C₁₀nitroalkyl,     C₁-C₁₀trialkylsilylalkyl, C₂-C₁₀alkylaminocarbonylalkyl,     C₂-C₁₀dialkylaminocarbonylalkyl, C₂-C₁₀alkylaminocarbonyloxyalkyl,     C₃-C₁₀dialkylaminocarbonyloxalkyl, C₂-C₁₀alkoxycarbonylaminoalkyl,     C₁-C₁₀—N-alkoxycarbonyl-N-alkylaminoalkyl, C₁-C₁₀cycloalkyl, aryl or     heteroaryl; or -   R₄ and R₅, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur and that, in     addition, may contain a fused or spiro-bound alkylene or alkenylene     chain consisting of from 2 to 6 carbon atoms, which chain may in     turn contain one or two hetero atoms selected from oxygen and     sulfur, wherein the cyclic group may be substituted by phenyl or     benzyl, which in turn may be substituted by halogen, C₁-C₆alkyl,     C₁-C₆haloalkyl, C₃-C₆cycloalkyl, hydroxy, C₁-C₆alkoxy,     C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro; -   R₂, R₆ and R₃₂ are each independently of the others C₁-C₁₀alkyl,     C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl,     C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl,     C₂-C₁₀alkylcarbonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; -   R₇, R₃₁ and R₃₃ are each independently of the others hydrogen,     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or C₂-C₁₀alkoxyalkyl; -   R₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl,     C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; or -   R₆ and R₇ or R₂ and R₃₁ or R₃₂ and R₃₃, together with the atom to     which they are bonded, form a saturated 3- to 7-membered cyclic     group that may contain one or two hetero atoms selected from     nitrogen, oxygen and sulfur; or R₆ and R₈, together with the atoms     to which they are bonded, form a 5- to 7-membered cyclic group that     may contain one or two hetero atoms selected from nitrogen, oxygen     and sulfur; -   R₉, R₁₀, R₁₁ and R₁₂ are each independently of the others     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; or -   R₉ and R₁₁ or R₉ and R₁₀, together with the atoms to which they are     bonded, form a 5- to 7-membered cyclic group that may contain one or     two hetero atoms selected from nitrogen, oxygen and sulfur; -   R₁₃, R₁₄, R₃₄ and R₃₅ are each independently of the others     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; or -   R₁₃ and R₁₄ or R₃₄ and R₃₅, together with the atoms to which they     are bonded, form a 5- to 7-membered cyclic group that may contain     one or two hetero atoms selected from nitrogen, oxygen and sulfur; -   R₁₅ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl,     C₂-C₁₀alkoxycarbonylalkyl, C₁-C₁₀aminoalkyl,     C₃-C₁₀dialkylaminoalkyl, C₂-C₁₀alkylaminoalkyl, C₁-C₁₀cyanoalkyl,     C₄-C₁₀cycloalkylalkyl, C₁-C₁₀phenylalkyl, C₁-C₁₀heteroarylalkyl,     C₁-C₁₀phenoxyalkyl, C₁-C₁₀heteroaryloxyalkyl, C₁-C₁₀nitroalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; -   R₁₆ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; -   R₁₇ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; -   R₁₈ is hydrogen, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀alkyl or     C₁-C₁₀alkoxyalkyl; or -   R₁₇ and R₁₈, together with the atoms to which they are bonded, form     a 3- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; -   Y is oxygen, sulfur, C—R₁₉ or N—R₃₆; -   R₁₉ and R₃₆ are each independently of the other C₁-C₁₀alkyl,     C₁-C₁₀haloalkyl, phenyl or heteroaryl; or -   R₁₈ and R₁₉ or R₁₈ and R₃₆, together with the atom to which they are     bonded, form a saturated 5- to 7-membered cyclic group that may     contain one or two hetero atoms selected from nitrogen, oxygen and     sulfur; -   G₁, G₂, G₃, G₄, G₅, G₆, G₇, G₈, G₉ and G₁₀ are each independently of     the others hydrogen, —C(X₁)—R₂₀, —C(X₂)—X₃—R₂₁, —C(X₄)—N(R₂₂)—R₂₃,     —SO₂—R₂₄, an alkali metal cation, alkaline earth metal cation,     sulfonium cation or ammonium cation, —P(X₅)(R₂₅)—R₂₆ or —CH₂—X₆—R₂₇; -   X₁, X₂, X₃, X₄, X₅ and X₆ are each independently of the others     oxygen or sulfur; -   R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the others hydrogen,     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,     C₁-C₅alkylamino-C₁-C₅alkyl, C₂-C₈dialkylamino-C₁-C₅alkyl,     C₃-C₇cycloalkyl-C₁-C₅alkyl, C₂-C₁₀alkoxyalkyl,     C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅alkylsulfonyl-C₁-C₅alkyl,     C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl,     C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅aminocarbonyl-C₁-C₅alkyl,     C₂-C₈dialkylaminocarbonyl-C₁-C₅alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,     C₁-C₅alkylcarbonyl-(C₂-C₅alkyl)-aminoalkyl,     C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl,     heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, or phenyl     substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or     heteroarylamino, or heteroaryl or heteroarylamino substituted by     C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,     cyano or by nitro, diheteroarylamino, or diheteroarylamino     substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, phenylamino, or     phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, diphenylamino, or     diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or     C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy; -   R₂₄, R₂₅ and R₂₆ are hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl,     C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl,     C₁-C₁₀aminoalkyl, C₁-C₅alkylamino-C₁-C₅alkyl,     C₂-C₈dialkylamino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl,     C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfoxyl-C₁-C₅alkyl,     C₁-C₅alkylsulfonyl-C₁-C₅alkyl, C₂-C₈alkylideneaminooxy-C₁-C₅alkyl,     C₁-C₅alkylcarbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl,     C₁-C₅aminocarbonyl-C₁-C₅alkyl, C₂-C₈dialkylaminocarbonyl-C₁-C₅alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,     C₁-C₅alkylcarbonyl-(C₂-C₅alkyl)-aminoalkyl,     C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl,     heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, or phenyl     substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or     heteroarylamino, or heteroaryl or heteroarylamino substituted by     C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,     cyano or by nitro, diheteroarylamino, or diheteroarylamino     substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, phenylamino, or     phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, diphenylamino, or     diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or     C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino, C₃-C₇cycloalkoxy,     C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, C₂-C₈dialkylamino,     benzyloxy or phenoxy, wherein the benzyl and phenyl groups may in     turn be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro; -   R₂₇ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,     C₁-C₅alkylamino-C₁-C₅alkyl, C₂-C₈dialkylamino-C₁-C₅alkyl,     C₃-C₇cycloalkyl-C₁-C₅alkyl, C₂-C₁₀alkoxyalkyl,     C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅alkylsulfonyl-C₁-C₅alkyl,     C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl,     C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅aminocarbonyl-C₁-C₅alkyl,     C₂-C₈dialkylaminocarbonyl-C₁-C₅alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₅alkyl,     C₁-C₅alkylcarbonyl-(C₂-C₅alkyl)-aminoalkyl,     C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl,     heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, or phenyl     substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or     heteroarylamino, or heteroaryl or heteroarylamino substituted by     C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,     cyano or by nitro, diheteroarylamino, diheteroarylamino substituted     by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,     halogen, cyano or by nitro, or phenylamino, phenylamino substituted     by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,     halogen, cyano or by nitro, diphenylamino, diphenylamino substituted     by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,     halogen, cyano or by nitro, C₃-C₇cycloalkylamino,     di-C₃-C₇cycloalkylamino, C₃-C₇cycloalkoxy or C₁-C₁₀alkylcarbonyl; -   Y₂ is oxygen, sulfur, C—R₁₄₀-R₁₄₁ or N—R₁₄₂, -   R₅₅ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,     C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl,     C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl,     C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; -   R₁₃₇ is hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or     C₁-C₁₀alkoxyalkyl; or R₅₅ and R₁₃₇, together with the atoms to which     they are bonded, form a 3- to 7-membered cyclic group that may     contain one or two hetero atoms selected from nitrogen, oxygen and     sulfur; -   R₁₃₈ and R₁₃₉ are each independently of the other hydrogen,     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or C₂-C₁₀alkoxyalkyl; and -   R₁₄₀ and R₁₄₁ are each independently of the other hydrogen,     C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or C₁-C₁₀alkoxyalkyl; or -   R₅₅ and C—R₁₄₀, together with the atoms to which they are bonded,     form a saturated or unsaturated 3- to 7-membered cyclic group that     may contain one or two hetero atoms selected from nitrogen, oxygen     and sulfur; -   R₁₄₂ is hydrogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl,     C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,     C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl,     C₃-C₁₀cycloalkyl, aryl or heteroaryl; or -   R₅₅ and N—R₁₄₂, together with the atoms to which they are bonded,     form a saturated or unsaturated 3- to 7-membered cyclic group that     may contain one or two hetero atoms selected from nitrogen, oxygen     and sulfur; -   and also to agronomically tolerable salts, isomers and enantiomers     of those compounds.

The alkyl groups occurring in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the isomers of pentyl, hexyl, heptyl, octyl, nonyl and decyl. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. Alkoxyalkyl is, for example, methoxymethyl, ethoxymethyl, propoxyethyl, isopropoxyethyl, n-butoxymethyl, isobutoxy-n-butyl, sec-butoxymethyl and tert-butoxyisopropyl, preferably methoxymethyl and ethoxymethyl. Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminoalkyl, phenylalkyl, nitroalkyl, aminoalkyl and N-alkoxycarbonyl-N-alkylaminoalkyl groups are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated. Alkenyl is to be understood as meaning, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl. Haloalkyl groups preferably have a chain length of from 1 to 4 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. Suitable haloalkenyl groups include alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine or iodine and especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Of the C₂-C₆alkenyl groups mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxy-carbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxy-carbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the butylamine isomers. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. Phenyl may be in substituted form. The substituents may in that case be in the ortho, meta and/or para position. Preferred substituents positions are the ortho and para positions relative to the point of attachment to the ring.

Aryl is, for example, phenyl or naphthyl. Those groups may also be substituted. When not specified otherwise in the definitions, phenyl, also as part of a substituent such as phenylalkyl, may, for example, be substituted by halogen, nitro, cyano, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfoxy, C₁-C₄alkylsulfonyl, carboxyl, C₁-C₄alkoxycarbonyl, amino, C₁-C₄alkylamino, C₁-C₄dialkylamino or by C₁-C₄alkylcarbonylamino.

Heteroaryl groups are usually aromatic heterocycles that contain preferably from 1 to 3 hetero atoms, such as nitrogen, sulfur and oxygen. Examples of suitable heterocycles and heteroaromatic compounds include: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetane, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and also pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzthiazole, quinoxaline and quinoline. Those heterocycles and heteroaromatic compounds may be further substituted, for example by halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, thioalkyl, alkylamino or by phenyl.

Within the scope of the present invention, 3- to 7-membered cyclic groups are to be understood as meaning ring systems that, in addition to the hetero atoms that may already be present in the ring of the substituent Q, may contain, besides the carbon atoms, one or more hetero atoms, such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. The unsaturated bond may, for example in the group Q₂, be formed by the substituents R₆ and R₇. Preferably, such ring systems contain from 5 to 7 ring atoms. 3- to 7-membered cyclic groups, including the cycloalkyls, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, may also be substituted. Suitable substituents include halogen, hydroxy, nitro, cyano, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, C₁-C₄alkyl, C₁-C₄haloalkyl, keto, C₂-C₄alkenyloxyimino, C₁-C₄alkoxy, C₁-C₄alkoxyalkoxy, C₁-C₄alkylthio, or one of the following three groups:

-   wherein X₈ is sulfur or oxygen, R₂₈ is C₁-C₄alkoxy or the two R₂₈     radicals, together with the —X₈—C—X₈ bridge to which they are     bonded, form a 5- or 6-membered ring that may be substituted by     methyl, ethyl, methoxy or by a keto group, -   R₂₉ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl or C₂-C₄haloalkenyl, -   R₃₀ and R₃₇ are each independently of the other C₁-C₄alkyl, phenyl     or C₂-C₄alkenyl, or R₃₀ and R₃₇, together with the nitrogen atom to     which they are bonded, form a 5- or 6-membered ring that may contain     a hetero atom selected from nitrogen, oxygen and sulfur.

In the substituent definitions, the number of carbon atoms is the total number of carbon atoms in the alkyl, alkenyl and alkynyl groups and the groups derived therefrom, for example haloalkyl or alkenyloxy. C₂-C₃Alkoxyalkyl accordingly comprises methoxymethyl, methoxyethyl and ethoxymethyl. C₃Alkoxycarbonylalkyl comprises methoxycarbonylethyl and ethoxycarbonylmethyl.

Alkali metal, alkaline earth metal or ammonium cations for the substituents G₁ to G₁₀ are, for example, the cations of sodium, potassium, magnesium, calcium and ammonium. Preferred sulfonium cations are especially trialkylsulfonium cations in which the alkyl groups preferably each contain from 1 to 4 carbon atoms.

Depending on the nature of the substituents, the compounds of formula I may also be in the form of geometric and/or optical isomers and mixtures of isomers as well as in the form of tautomers and mixtures of tautomers. The present invention relates also to those compounds of formula 1. For example, the compounds of formula I wherein Q is Q₁ and the group G₁ is hydrogen may be present in the following tautomeric equilibria:

When G₁ to G₁₀ is other than hydrogen and the cyclic group formed by R₄ and R₅ together is asymmetrically substituted, fused or spiro-bound, for example the compound of formula I may be present in the form of an isomer of formula Id

The invention likewise includes the salts that the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt formers are described, for example, in WO 98/41089.

The invention likewise includes the salts that the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.

Of the alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn to the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially to those of sodium or potassium.

Examples of amines suitable for ammonium salt formation include both ammonia and also primary, secondary and tertiary C₁-C₁₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for the salt formation correspond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OH, wherein R_(a), R_(b), R_(c), and R_(d) are each independently of the others C₁-C₄ alkyl. Other suitable tetraalkylammonium bases having other anions can be obtained, for example, by anion exchange reactions.

Of the compounds of formula I, preference is given to those wherein Q is Q₁, Q₂, Q₃, Q₄, Q₅, Q₆, Q₇, Q₈ or Q₉.

Preference is given also to compounds of formula I wherein R₄ and R₅ are each independently of the other C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₄-C₆alkenyloxyalkyl, C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthioalkyl, C₂-C₆alkylsulfoxylalkyl, C₂-C₆alkylsulfonylalkyl, C₂-C₆alkylcarbonylalkyl, C₃-C₆-N-alkoxy-iminoalkyl, C₃-C₆alkoxycarbonylalkyl, C₁-C₆aminoalkyl, C₂-C₆dialkylaminoalkyl, C₃-C₆alkylaminoalkyl, C₁-C₆cyanoalkyl, C₄-C₈cycloalkylalkyl, C₇-C₈phenylalkyl, C₇-C₈heteroarylalkyl, C₇-C₈phenoxyalkyl, C₇-C₈heteroaryloxyalkyl, C₄-C₆alkylideneaminooxyalkyl, C₁-C₆nitroalkyl, C₄-C₈trialkylsilylalkyl, C₄-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₄-C₈alkylaminocarbonyloxyalkyl, C₄-C₈dialkylaminocarbonyloxalkyl, C₄-C₈alkoxycarbonylaminoalkyl, C₄-C₈-N-alkoxycarbonyl-N-alkylaminoalkyl, C₃-C₈cycloalkyl, aryl or heteroaryl, or

-   R₄ and R₅, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group.

Preference is given also to compounds of formula I wherein

-   R₂, R₆ and R₃₂ are each independently of the others C₁-C₆alkyl,     C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₄-C₆alkenyloxyalkyl,     C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthioalkyl, C₂-C₆alkylsulfoxylalkyl,     C₂-C₆alkylsulfonylalkyl, C₃-C₆alkylcarbonylalkyl, C₃-C₈cycloalkyl,     aryl or heteroaryl; -   R₇, R₃₁ and R₃₃ are hydrogen, C₁-C₆alkyl or C₁-C₆alkoxyalkyl; -   R₈ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₄-C₆alkenyloxyalkyl, C₄-C₆alkynyloxyalkyl, C₁-C₆alkylthioalkyl,     C₁-C₆alkylsulfinylalkyl, C₁-C₆alkylsulfonylalkyl, C₃-C₈cycloalkyl,     aryl or heteroaryl; or -   R₆ and R₇ or R₂ and R₃₁ or R₃₂ and R₃₃, together with the atoms to     which they are bonded, form a 5- to 7-membered cyclic group that may     contain one or two hetero atoms selected from nitrogen, oxygen and     sulfur, or -   R₆ and R₈, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; -   R₉, R₁₀, R₁₁, and R₁₂ are each independently of the others     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₈alkoxyalkyl, C₄-C₆alkenyloxyalkyl,     C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthialkyl, C₂-C₆alkylsulfinylalkyl,     C₂-C₆alkylsulfonylalkyl, C₃-C₆alkylcarbonylalkyl, C₃-C₈cycloalkyl,     aryl or heteroaryl; or -   R₉ and R₁₁ or R₉ and R₁₀, together with the atoms to which they are     bonded, form a 5- to 7-membered cyclic group that may contain one or     two hetero atoms selected from nitrogen, oxygen and sulfur, or -   R₉ and R₁₀, together with the atom to which they are bonded, form a     saturated 3- to 7-membered cyclic group that may contain one or two     hetero atoms selected from nitrogen, oxygen and sulfur; -   R₁₃, R₁₄, R₃₄ and R₃₅ are each independently of the others     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₄-C₆alkenyloxyalkyl.     C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthioalkyl, C₂-C₆alkyl sulfoxylalkyl,     C₂-C₆alkylsulfonylalkyl, C₃-C₆alkylcarbonylalkyl, C₃-C₈cycloalkyl,     aryl or heteroaryl; or -   R₁₃ and R₁₄ or R₃₄ and R₃₅, together with the atoms to which they     are bonded, form a 5 to 7-membered cyclic group that may contain one     or two hetero atoms selected from nitrogen, oxygen and sulfur, -   R₁₅ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₄-C₆alkenyloxyalkyl, C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthioalkyl,     C₂-C₆alkylsulfoxylalkyl, C₂-C₆alkylsulfonylalkyl,     C₃-C₆alkylcarbonylalkyl, C₃-C₆alkoxycarbonylalkyl, C₂-C₆aminoalkyl,     C₄-C₆dialkylaminoalkyl, C₄-C₆alkylaminoalkyl, C₂-C₆cyanoalkyl,     C₃-C₈cycloalkylalkyl, C₇-C₈phenylalkyl, C₇-C₈heteroarylalkyl,     C₇-C₈phenoxyalkyl, C₆-C₈heteroaryloxyalkyl, C₁-C₆nitroalkyl,     C₃-C₈cycloalkyl, aryl or heteroaryl; -   R₁₆ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₄-C₆alkenyloxyalkyl, C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthiolkyl,     C₂-C₆alkylsulfinylalkyl, C₂-C₆alkylsulfonylalkyl, C₃-C₈cycloalkyl,     aryl or heteroaryl; -   R₁₇ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₄-C₆alkenyloxyalkyl, C₄-C₆alkynyloxyalkyl, C₂-C₆alkylthialkyl,     C₂-C₆alkylsulfinylalkyl, C₂-C₆alkylsulfonylalkyl,     C₃-C₆alkylcarbonylalkyl, C₃-C₈cycloalkyl, aryl or heteroaryl; -   R₁₈ is hydrogen, C₁-C₆alkyl or C₂-C₆alkoxyalkyl; or -   R₁₇ and R₁₈, together with the atoms to which they are bonded, form     a 3- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur, -   R₁₉ and R₃₆ are each independently of the other C₁-C₆alkyl,     C₁-C₆haloalkyl, phenyl or heteroaryl; or -   R₁₈ and R₁₉ or R₁₈ and R₃₆, together with the atom to which they are     bonded, form a saturated 5- to 7-membered cyclic group that may     contain one or two hetero atoms selected from nitrogen, oxygen and     sulfur, -   R₂₀, R₂₁, R₂₂, R₂₃ and R₂₇ are each independently of the others     hydrogen, C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl,     C₁-C₈nitroalkyl, C₁-C₈aminoalkyl, C₁-C₅alkylamino-C₁-C₂alkyl,     C₂-C₆dialkylamino-C₁-C₂alkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, C₄-C₈alkenyloxyalkyl, C₄-C₈alkynyloxyalkyl,     C₂-C₈alkylthioalkyl, C₁-C₂alkylsulfoxyl-C₁-C₂alkyl,     C₁-C₂alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂alkyl,     C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₅alkoxycarbonyl-C₁-C₂alkyl,     C₁-C₅amino-carbonyl-C₁-C₂alkyl,     C₂-C₈dialkylamino-carbonyl-C₁-C₂alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,     C₁-C₂alkylcarbonyl-N—C₁-C₃alkyl-C₁-C₂aminoalkyl,     C₃-C₆-trialkylsilyl-C₁-C₃alkyl, phenyl-C₁-C₂alkyl,     heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or     heteroaryl; -   R₂₄, R₂₅ and R₂₆ are each independently of the others hydrogen,     C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl, C₁-C₈nitroalkyl,     C₁-C₈aminoalkyl, C₁-C₅alkylamino-C₁-C₂alkyl,     C₂-C₆dialkylamino-C₁-C₂alkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, C₄-C₈alkenyloxyalkyl, C₄-C₈alkynyloxyalkyl,     C₂-C₈alkylthioalkyl, C₁-C₂alkylsulfoxyl-C₁-C₂alkyl,     C₁-C₂alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂alkyl,     C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₅alkoxycarbonyl-C₁-C₂alkyl,     C₁-C₅amino-carbonyl-C₁-C₂alkyl,     C₂-C₈dialkylamino-carbonyl-C₁-C₂alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,     C₁-C₂alkylcarbonyl-N—C₁-C₃alkyl-C₁-C₂aminoalkyl,     C₃-C₆trialkylsilyl-C₁-C₃alkyl, phenyl-C₁-C₂alkyl,     heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, heteroaryl,     C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₃alkylamino, C₂-C₆dialkylamino, or     benzyloxy or phenoxy in which the benzyl and phenyl groups may in     turn be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,     C₁-C₃haloalkoxy, halogen, cyano or by nitro; and -   R₂₇ is C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈cyanoalkyl, C₁-C₈nitroalkyl,     C₁-C₈aminoalkyl, C₁-C₅alkylamino-C₁-C₂alkyl,     C₂-C₆dialkylamino-C₁-C₂alkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, C₄-C₈alkenyloxyalkyl, C₄-C₈alkynyloxyalkyl,     C₂-C₈alkylthioalkyl, C₁-C₂alkylsulfoxyl-C₁-C₂alkyl,     C₁-C₂alkylsulfonyl-C₁-C₂alkyl, C₂-C₈alkylideneaminooxy-C₁-C₂alkyl,     C₁-C₅alkylcarbonyl-C₁-C₂alkyl, C₁-C₅alkoxycarbonyl-C₁-C₂alkyl,     C₁-C₅amino-carbonyl-C₁-C₂alkyl,     C₂-C₈dialkylamino-carbonyl-C₁-C₂alkyl,     C₁-C₅alkylcarbonylamino-C₁-C₂alkyl,     C₁-C₂alkylcarbonyl-N—C₁-C₃alkyl-C₁-C₂aminoalkyl,     C₃-C₆trialkylsilyl-C₁-C₃alkyl, phenyl-C₁-C₂alkyl,     heteroaryl-C₁-C₂alkyl, phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl,     C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, heteroaryl,     C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₈alkylcarbonyl, C₁-C₃alkylamino,     C₂-C₆dialkylamino, or benzyloxy or phenoxy in which the benzyl and     phenyl groups may in turn be substituted by C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by     nitro.

Special preference is given to compounds of formula I wherein

-   R₁ and R₃ are each independently of the other ethyl, haloethyl,     ethynyl, C₁-C₂alkoxy, C₁-C₂haloalkoxy or C₁-C₂alkylcarbonyl; -   R₄ and R₅ are each independently of the other C₁-C₆alkyl,     C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₂-C₆alkylcarbonylalkyl,     C₃-C₆alkoxycarbonylalkyl, C₁-C₆aminoalkyl, C₂-C₆dialkylaminoalkyl,     C₃-C₆alkylaminoalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, aryl or     heteroaryl; or -   R₄ and R₅, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; -   R₂, R₆ and R₃₂ are each independently of the others C₁-C₆alkyl,     C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₃-C₈cycloalkyl, aryl or     heteroaryl; -   R₇, R₃₁ and R₃₃ are each independently of the others hydrogen,     C₁-C₆alkyl or C₁-C₆alkoxyalkyl; -   R₈ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₁-C₆alkylthioalkyl, C₃-C₈cycloalkyl, aryl or heteroaryl; or -   R₆ and R₇ or R₂ and R₃₁ or R₃₂ and R₃₃, together with the atom to     which they are bonded, form a saturated 3- to 7-membered cyclic     group that may contain one or two hetero atoms selected from     nitrogen, oxygen and sulfur; or -   R₆ and R₈, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; -   R₉, R₁₀, R₁₁, and R₁₂ are each independently of the others     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl, C₃-C₈cycloalkyl, aryl     or heteroaryl; or -   R₉ and R₁₁, together with the atoms to which they are bonded, form a     5- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; or -   R₉ and R₁₀, together with the atom to which they are bonded, form a     saturated 3- to 7-membered cyclic group that may contain one or two     hetero atoms selected from nitrogen, oxygen and sulfur; -   R₁₃, R₁₄, R₃₄ and R₃₅ are each independently of the others     C₁-C₆alkyl, C₃-C₈cycloalkyl, aryl or heteroaryl; or -   R₁₃ and R₁₄ or R₃₄ and R₃₅, together with the atoms to which they     are bonded, form a 5- to 7-membered cyclic group that may contain     one or two hetero atoms selected from nitrogen, oxygen and sulfur; -   R₁₅ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₄-C₆alkenyloxyalkyl, C₂-C₆alkylthioalkyl, C₂-C₆alkylsulfoxylalkyl,     C₃-C₆alkoxycarbonylalkyl, C₃-C₈cycloalkyl, aryl or heteroaryl; -   R₁₆ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkoxyalkyl,     C₃-C₈cycloalkyl, aryl or heteroaryl; -   R₁₇ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₈cycloalkyl, aryl or     heteroaryl; -   R₁₈ is hydrogen, C₁-C₆alkyl or C₂-C₆alkoxyalkyl; or -   R₁₇ and R₁₈, together with the atoms to which they are bonded, form     a 3- to 7-membered cyclic group that may contain one or two hetero     atoms selected from nitrogen, oxygen and sulfur; -   R₁₉ and R₃₆ are each independently of the other C₁-C₆alkyl or     C₁-C₆haloalkyl; or -   R₁₈ and R₁₉ or R₁₈ and R₃₆, together with the atom to which they are     bonded, form a saturated 5- to 7-membered cyclic group that may     contain one or two hetero atoms selected from nitrogen, oxygen and     sulfur; -   R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the others hydrogen,     C₁-C₈alkyl, C₁-C₆haloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,     phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl, C₂-C₅alkenyl,     C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or heteroaryl; -   R₂₄, R₂₅ and R₂₆ are each independently of the others hydrogen,     C₁-C₈alkyl, C₁-C₈haloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,     phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl, C₂-C₅alkenyl,     C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, heteroaryl, C₁-C₆alkoxy,     C₁-C₃alkylamino or C₂-C₆dialkylamino; and -   R₂₇ is C₁-C₈alkyl, C₁-C₈haloalkyl, C₃-C₇cycloalkyl-C₁-C₂alkyl,     C₂-C₈alkoxyalkyl, phenyl-C₁-C₂alkyl, heteroaryl-C₁-C₂alkyl,     phenoxy-C₁-C₂alkyl, heteroaryloxy-C₁-C₂alkyl, C₂-C₅alkenyl,     C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, heteroaryl, C₁-C₆alkoxy,     C₁-C₃alkylamino, C₂-C₆dialkylamino or C₁-C₈alkylcarbonyl.

The compounds of formula I can be prepared by reacting a compound of formula XXX Q—H  (XXX) wherein Q is Q₁, Q₂, Q₃, Q₄, Q₅, Q₆, Q₇, Q₈, Q₉ or Q₁₀, the substituents of which, with the exception of G₁, G₂, G₃, G₄, G₅, G₆, G₇, G₈, G₉ and G₁₀, have the meanings given above, and G₁, G₂, G₃, G₄, G₅, G₆, G₇, G₈, G₉ and G₁₀ are hydrogen, with a compound of formula XXXI

wherein R₁ and R₃ are as defined for formula I and Hal is chlorine, bromine or iodine, in the presence of an inert solvent, a base and a palladium catalyst, at temperatures of from 30 to 250° C. The reaction is preferably carried out under an inert gas atmosphere.

Surprisingly, it has been shown that this process is very especially advantageous for the preparation of compounds of formula I wherein R₁ and R₃ are ethyl. The intermediates of formula XXXI wherein R₁ and R₃ are ethyl and HaI is chlorine, bromine or iodine (formula XXXIa) used for the preparation of those compounds of formula I are novel and were developed especially for that process. The present invention accordingly also relates to those intermediates.

The compounds of formula XXX are known or can be prepared according to known processes, as described, for example, in J. Chem. Soc. Perkin Trans. 1 (1987), (4), 877-884. The compounds of formula XXXI can be prepared, for example, according to known methods, via the diazonium salts, for example by Sandmeyer reaction starting from the corresponding anilines of formula XXXII

wherein R₁ and R₃ are as defined for formula I. Such reactions are described, for example, in Vogel's Textbook of Practical Organic Chemistry, 5th Edition, B. S. Furniss, A. J. Hannaford, P. W. G. Smith, A. R. Tatchell; Longman Scientific & Technical 1989, page 923. The compounds of formula XXXII are known; some of them are available commercially or they can be prepared analogously to known methods.

There are suitable for the reaction bases such as trialkali metal phosphates, alkali metal and alkaline earth metal hydrides, alkali metal and alkaline earth metal amides or alkali metal alcoholates, for example tripotassium phosphate, sodium hydride, lithium diisopropylamide (LDA), sodium tert-butanolate or potassium tert-butanolate. Sodium tert-butanolate, potassium tert-butanolate and tripotassium phosphate are especially preferred.

Suitable solvents include, for example, aromatic hydrocarbons, for example xylene or toluene, ethers, such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, dimethyl sulfoxide or tertiary amides, such as dimethylformamide, N-methylpyrrolidinone or dimethyl acetamide, and acyclic ureas, such as N,N′-dimethylpropyleneurea.

Palladium catalysts that come into consideration for the C—C coupling reaction of a compound of formula XXX with a compound of formula XXXI are generally palladium(II) or palladium(0) complexes, for example palladium(II) dihalides, palladium(II) acetate, palladium(II) sulfate, bis(triphenylphosphine)palladium(II) dichloride, bis(tricyclopentylphosphine)palladium(II) dichloride, bis(tricyclohexylphosphine)palladium(II) dichloride, bis(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphosphine)palladium(0). The palladium catalyst can also be prepared “in situ” from palladium(II) or palladium(0) compounds by complexing with the desired ligands, by, for example, combining the palladium(II) salt to be complexed, for example palladium(II) dichloride (PdCl₂) or palladium(II) acetate (Pd(OAc)₂), together with the desired ligand, for example triphenylphosphine (PPh₃), tricyclopentylphosphine or tricyclohexylphosphine and the selected solvent, with a compound of formula XXXI, a compound of formula XXX and a base. Also suitable are bidendate ligands, for example 1,1′-bis(diphenylphosphino)ferrocene or 1,2-bis(diphenylphosphino)ethane. By heating the reaction medium, the palladium(II) complex or palladium(0) complex desired for the C—C coupling reaction is thus formed “in situ”, and then initiates the C—C coupling reaction.

The palladium catalysts are used in an amount of from 0.001 to 50 mol %, preferably in an amount of from 0.1 to 15 mol %, based on the compound of formula XXXI.

The reaction temperatures are selected in accordance with the solvent used and, where applicable, in accordance with the pressure. Preferably, the reaction is carried out at atmospheric pressure.

The compounds of formula I wherein Q is Q₁ can be prepared analogously to the procedures described in WO 96/21652. Compounds of formula I wherein Q is Q₂ can be prepared, for example, in accordance with the procedures described in EP-A-0 415 185, EP-A-0 521 334, EP-A-0 355 599 and EP-A-0 442 077. Compounds of formula I wherein Q is Q₃, Q₄, Q₆ or Q₇ can be prepared, for example, in accordance with the procedures described in WO 96/35644 and WO 97/02243. Compounds of formula I wherein Q is Q₅ can be prepared, for example, analogously to the procedures described in WO 97/14667. Analogous procedures for the preparation of compounds of formula I wherein Q is Q₇ are described in WO 97/16436. Compounds of formula I in which Q is Q₈ can be prepared analogously to U.S. Pat. No. 5,994,274. Compounds of formula I wherein Q is Q₉ can be prepared analogously to JP 11152273 A (priority: 19.11.1997 JP 318614), Compounds of formula I wherein Q is Q₁₀ can be prepared according to J. Org. Chem. (1979), 44(26), 4906-4912 or J. Org. Chem. (1977), 42(7), 1163-1169 or in an analogous manner.

The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitrites, such as acetonitrile or propionitrile, and amides, such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from −20° C. to +120° C. The reactions are generally slightly exothermic and can usually be carried out at room temperature. To shorten the reaction time or also to initiate the reaction, the temperature can, if desired, be increased to the boiling point of the reaction mixture for a brief period. The reaction times can also be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases include especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene and 1,5-diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, for example sodium or calcium hydride, hydroxides, for example sodium or potassium hydroxide, carbonates, for example sodium or potassium carbonate, or hydrogen carbonates, for example potassium or sodium hydrogen carbonate.

The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

For the use in accordance with the invention of the compounds of formula I or of compositions comprising them, there are suitable any of the methods of application customary in agriculture, such as pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques, for example the controlled release of active ingredient. In that method, the active ingredient is applied in solution to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. Where appropriate, it is also possible to apply a coating (coated granules) that allows the active ingredient to be released in metered amounts over a specific period.

The compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis. Preferably, however, they are formulated in customary manner using the adjuvants customarily employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures comprising the active ingredient of formula I or at least one active ingredient of formula I and generally one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, it is also possible for surface-active compounds (surfactants) to be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485 on page 6.

Depending on the nature of the active ingredient of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Vertag, Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81.

The activity of the herbicidal and plant growth-inhibiting compositions according to the invention comprising a herbicidally effective amount of compound of formula I can be increased by the addition of spray tank adjuvants.

Such adjuvants may be, for example: non-ionic surfactants, mixtures of non-ionic surfactants, mixtures of anionic surfactants with non-ionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with and without surfactants, vegetable oil derivatives with and without the addition of surfactant, alkylated derivatives of oils of vegetable or mineral origin with and without surfactants, fish oils and other animal oils of animal nature and alkyl derivatives thereof with and without surfactants, naturally occurring higher fatty acids, preferably having from 8 to 28 carbon atoms, and alkyl ester derivatives thereof, organic acids containing an aromatic ring system and one or more carboxylic acid esters, and alkyl derivatives thereof, and also suspensions of polymers of vinyl acetate or of copolymers of vinyl acetate/acrylic acid esters. Mixtures of individual adjuvants with one another and combined with organic solvents may lead to the activity being further increased.

Suitable non-ionic surfactants include, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and alkylphenols, preferably that can contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and from 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts of polypropylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having preferably from 1 to 10 carbon atoms in the alkyl chain, which adducts contain preferably from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups. The said compounds usually contain from 1 to 5 ethylene glycol units per propylene glycol unit.

There may also be mentioned, as further examples of non-ionic surfactants, nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylenesorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable.

Preferred anionic surfactants are especially alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids, and ethoxylated derivatives thereof. The alkyl radicals usually contain from 8 to 24 carbon atoms.

Preferred non-ionic surfactants are known by the following trade names:

-   polyoxyethylene cocoalkylamine (e.g. AMIET® 105 (Kao Co.)),     polyoxyethylene oleylamine (e.g. AMIET® 415 (Kao Co.)), nonylphenol     polyethoxyethanols, polyoxyethylene stearylamine (e.g. AMIET® 320     (Kao Co.)), N-polyethoxyethylamines (e.g. GENAMIN® (Hoechst AG)),     N,N,N′,N′-tetra(polyethoxypolypropoxyethyl)ethylene-diamine (e.g.     TERRONIL® and TETRONIC® (BASF Wyandotte Corp.)), BRIJ® (Atlas     Chemicals), ETHYLAN® CD and ETHYLAN® D (Diamond Shamrock), GENAPOL®     C, GENAPOL® O, GENAPOL® S and GENAPOL® X080 (Hoechst AG), EMULGEN®     104P, EMULGEN® 109P and EMULGEN® 408 (Kao Co.); DISTY® 125     (Geronazzo), SOPROPHOR® CY 18 (Rhone Poulenc S.A.); NONISOL®     (Ciba-Geigy), MRYJ® (ICI); TWEEN® (ICI); EMULSOGEN® (Hoechst AG);     AMIDOX® (Stephan Chemical Co.), ETHOMID® (Armak Co.); PLURONIC®     (BASF Wyandotte Corp.), SOPROPHOR® 461P (Rhone Poulenc S.A.),     SOPROPHOR® 496/P (Rhone Poulenc S.A.), ANTAROX FM-63 (Rhone Poulenc     S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N     (Osi-Specialities).

The cationic surfactants are especially quaternary ammonium salts that contain as N-substituent(s) at least one alkyl radical having from 8 to 22 carbon atoms and, as further substituents, optionally halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The oils used are either of mineral or natural origin. The natural oils can in addition be of animal or vegetable origin. Of the animal oils preference is given especially to derivatives of beef tallow, but fish oils (e.g. sardine oil) and derivatives thereof are also used. Vegetable oils are mostly seed oils of varied origin. Examples of vegetable oils used especially that may be mentioned include coconut oil, rapeseed oil and sunflower oil and derivatives thereof.

In the composition according to the invention, the concentrations of oil additive are generally from 0.01 to 2%, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.

Preferred oil additives in the composition according to the invention comprise an oil of vegetable origin, for example rapeseed oil or sunflower oil, alkyl esters of oils of vegetable origin, for example methyl derivatives, or mineral oils.

Especially preferred oil additives comprise alkyl esters of higher fatty acids (C₈-C₂₂), especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).

The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.

Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also nonionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland).

The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30% by weight.

Examples of oil additives consisting of mixtures of oils or mineral oils or derivatives thereof with surfactants include Edenor ME SU®, Emery 2231® (Henkel subsidiary Cognis GMBH, DE), Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) or, more especially, Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can, furthermore, bring about a further increase in activity. Suitable solvents include, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types.

The concentration of such solvents can be from 10 to 80%, by weight, of the total weight.

Such oil additives, which, for example, are also described in U.S. Pat. No. 4,834,908, are especially preferred for the composition according to the Invention. A more especially preferred oil additive is known by the name MERGE®, can be obtained from BASF Corporation and is basically described, for example, in U.S. Pat. No. 4,834,908, col. 5, as Example COC-1. A further oil additive that is preferred in accordance with the invention is SCORE® (Novartis Crop Protection Canada).

Surfactants, oils, especially vegetable oils, derivatives thereof, such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants, such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and also higher fatty acids, that are customary in formulation and adjuvant technology and that can also be used in the compositions according to the invention and in spray tank solutions thereof, are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1998, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, “A Compendium of Herbicide Adjuvants”, Southern Illinois Univ., 1998, L. Thomson Harvey, “A Guide to Agricultural Spray Adjuvants Used in the United States”, Thomson Pubns., 1992.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, especially from 5 to 99.8% by weight, of a solid or liquid formulation adjuvant, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and also fertilisers or other active ingredients.

The active ingredients of formula I are generally used on the plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the type of action, the development stage of the crop plant and of the weed and on the application (place, time, method) and, in dependence on those parameters, can vary within wide ranges.

The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties that make them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and for non-selective weed control. Crops are also to be understood as including those that have been rendered tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods. Those include, for example, IMI Maize, Poast Protected Maize (sethoxydim tolerance), Liberty Link Maize, B.t./Liberty Link Maize, IMI/Liberty Link Maize, IMI/Liberty Link /B.t. Maize, Roundup Ready Maize and Roundup Ready/B.t. Maize.

The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

Surprisingly, it has been shown that special safeners, known from U.S. Pat. No. 5,041,157, U.S. Pat. No. 5,541,148, U.S. Pat. No. 5,006,656, EP-A-0 094 349, EP-A-0 551 650, EP-A-0 268 554, EP-A-0 375 051, EP-A-0 174 562, EP-A-492 366, WO 91/7874, WO 94/987, DE-A-19612943, WO 96/29870, WO 98/13361, WO 98/39297, WO 98/27049, EP-A-0 716 073, EP-A0 613 618, U.S. Pat. No. 5,597,776, EP-A-0 430 004, DE-A-4 331 448, WO 99/16744, WO 00/30447 and WO 00/00020, are suitable for mixing with the herbicidal compositions according to the invention. The present invention accordingly relates also to a selective-herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of maize and cereals, which composition comprises a herbicide of formula I and a safener (antidote) and protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, and to the use of such a composition in the control of weeds in crops of useful plants.

There is thus proposed, in accordance with the invention, a selective-herbicidal composition that comprises as active ingredient, in addition to customary inert formulation adjuvants, such as carriers, solvents and wetting agents, a mixture of

-   a) a herbicidally effective amount of a compound of formula I -    wherein R₁, R₃ and Q are as defined hereinabove, with the proviso     that Q is other than Q₁; and -   b) a herbicide-antagonistically effective amount either of a     compound of formula X -    wherein -   R₃₇ is hydrogen, C₁-C₈alkyl, or C₁-C₈alkyl substituted by     C₁-C₆alkoxy or by C₃-C₆alkenyloxy; -   and X₇ is hydrogen or chlorine; or of a compound of formula XI -    wherein E is nitrogen or methine; -   R₃₈ is —CCl₃, phenyl or phenyl substituted by halogen; -   R₃₉ and R₄₀ are each independently of the other hydrogen or halogen;     and -   R₄₁ is C₁-C₄alkyl; or of a compound of formula XII -    wherein R₄₄ and R₄₅ are each independently of the other hydrogen or     halogen, and R₄₆, R₄₇ and R₄₈ are each independently of the others     C₁-C₄alkyl, or of a compound of formula XIII -    wherein A₂ is a group -    R₅₁ and R₅₂ are each independently of the other hydrogen,     C₁-C₈alkyl, C₃-C₈cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, -    or C₁-C₄alkyl substituted by C₁-C₄alkoxy or by -    or R₅₁ and R₅₂ together form a C₄-C₆alkylene bridge that may be     interrupted by oxygen, sulfur, SO, SO₂, NH or by —N(C₁-C₄alkyl)-; -   R₅₃ is hydrogen or C₁-C₄alkyl; -   R₄₉ is hydrogen, halogen, cyano, trifluoromethyl, nitro, C₁-C₄alkyl,     C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,     —COOR_(j), —CONR_(k)R_(m), —COR_(n), —SO₂NR_(k)R_(m) or     —OSO₂—C₁-C₄alkyl; -   R₉ is hydrogen, halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄haloalkyl,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —COOR_(j),     —CONR_(k)R_(m), —COR_(n), SO₂NR_(k)R_(m), —OSO₂—C₁-C₄alkyl,     C₁-C₆alkoxy, or C₁-C₆alkoxy substituted by C₁-C₄alkoxy or by     halogen, C₃-C₆alkenyloxy, or C₃-C₆alkenyloxy substituted by halogen,     or C₃-C₆alkynyloxy, or R₄₉ and R₅₀ together form a C₃-C₄alkylene     bridge that may be substituted by halogen or by C₁-C₄alkyl, or     together form a C₃-C₄alkenylene bridge that may be substituted by     halogen or by C₁-C₄alkyl, or together form a C₄alkadienylene bridge     that may be substituted by halogen or by C₁-C₄alkyl; -   R₅₀ and R_(h) are each independently of the other hydrogen, halogen,     C₁-C₄alkyl, trifluoro-methyl, C₁-C₆alkoxy, C₁-C₆alkylthio or     —COOR_(j); -   R_(c) is hydrogen, halogen, nitro, C₁-C₄alkyl or methoxy; R_(d) is     hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,     C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —COOR_(j) or CONR_(k)R_(m); -   R_(e) is hydrogen, halogen, C₁-C₄alkyl, —COOR_(j), trifluoromethyl     or methoxy, or R_(d) and R_(e) together form a C₃-C₄alkylene bridge; -   Rp is hydrogen, halogen, C₁-C₄alkyl, —COOR_(j), trifluoromethyl or     methoxy; Rq is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄alkoxy,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —COOR_(j) or     CONR_(k)R_(m); or Rp and Rq together form a C₃-C₄alkylene bridge; -   Rr is hydrogen, halogen, C₁-C₄alkyl, —COOR_(j), trifluoromethyl or     methoxy; Rs is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄alkoxy,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —COOR_(j) or     CONR_(k)R_(m); or Rr and Rs together form a C₃-C₄alkylene bridge; -   Rt is hydrogen, halogen, C₁-C₄alkyl, —COOR_(j), trifluoromethyl or     methoxy; Ru is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄alkoxy,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —COOR_(j) or     CONR_(k)R_(m), or Rv and Ru together form a C₃-C₄alkylene bridge; -   R_(l) and Rv are hydrogen, halogen or C₁-C₄alkyl; -   R_(x) and R_(y) are each independently of the other hydrogen,     halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, —COOR₅₄,     trifluoromethyl, nitro or cyano; -   R_(j), R_(k) and R_(m) are each independently of the others hydrogen     or C₁-C₄alkyl; or R_(k) and R_(m) together form a C₄-C₆alkylene     bridge that may be interrupted by oxygen, NH or by —N(C₁-C₄alkyl)-; -   R_(n) is C₁-C₄alkyl, phenyl, or phenyl substituted by halogen,     C₁-C₄alkyl, methoxy, nitro or by trifluoromethyl; -   R₅₄ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,     C₁-C₄alkylthio-C₁-C₄alkyl, di-C₁-C₄alkylamino-C₁-C₄alkyl,     halo-C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl,     C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl,     allylcarbonyl, C₃-C₇cycloalkyl-carbonyl, benzoyl, which is     unsubstituted or substituted on the phenyl ring identically or     differently up to three times by halogen, C₁-C₄alkyl,     halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy or C₁-C₄alkoxy; or furoyl,     thienyl; or C₁-C₄alkyl substituted by phenyl, halophenyl,     C₁-C₄alkylphenyl, C₁-C₄alkoxyphenyl, halo-C₁-C₄alkylphenyl,     halo-C₁-C₄alkoxyphenyl, C₁-C₆alkoxy-carbonyl,     C₁-C₄alkoxy-C₁-C₈alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl,     C₃-C₈alkynyloxy-carbonyl, C₁-C₈alkylthiocarbonyl,     C₃-C₈alkenylthiocarbonyl, C₃-C₈alkynylthiocarbonyl, carbamoyl,     mono-C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkylaminocarbonyl; or     phenylaminocarbonyl, which is unsubstituted or substituted on the     phenyl identically or differently up to three times by halogen,     C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy or C₁-C₄alkoxy or once     by cyano or nitro; or dioxolan-2-yl, which is unsubstituted or     substituted by one or two C₁-C₄alkyl radicals, or dioxan-2-yl, which     is unsubstituted or substituted by one or two C₁-C₄alkyl radicals,     or C₁-C₄alkyl substituted by cyano, nitro, carboxyl or by     C₁-C₈alkylthio-C₁-C₈alkoxy-carbonyl; -   or of a compound of formula XIV -    wherein R₅₈ and R₅₇ are each independently of the other C₁-C₆alkyl     or C₂-C₆alkenyl; or R₅₆ and R₅₇ together are -    R₅₈ and R₅₉ are each independently of the other hydrogen or     C₁-C₆alkyl; or R₅₆ and R₅₇ together are -   R₆₀ and R₆₁ are each independently of the other C₁-C₄alkyl, or R₆₀     and R₆₁ together are —(CH₂)₅—; -   R₆₂ is hydrogen, C₁-C₄alkyl or -    or R₅₆ and R₅₇ together are -   R₆₃, R₆₄, R₆₅, R₆₆, R₆₇, R₆₈, R₆₉, R₇₀, R₇₁, R₇₂, R₇₃, R₇₄, R₇₅,     R₇₆, R₇₇ and R₇₈ are each independently of the others hydrogen or     C₁-C₄alkyl; or of a compound of formula XV -    wherein R₈₀ is hydrogen or chlorine and R₇₉ is cyano or     trifluoromethyl; or of a compound of formula XVI -    wherein R₈₁ is hydrogen or methyl; -   or of a compound of formula XVII -    wherein -   R₈₂ is hydrogen, C₁-C₄alkyl, or C₁-C₄alkyl substituted by     C₁-C₄alkyl-X₂— or by C₁-C₄haloalkyl-X₂—, or is C₁-C₄haloalkyl,     nitro, cyano, —COOR₈₅, —NR₈₆R₈₇, —SO₂NR₈₈R₈₉ or —CONR₉₀R₉₁; -   R₈₃ is hydrogen, halogen, C₁-C₄alkyl, trifluoromethyl, C₁-C₄alkoxy     or C₁-C₄haloalkoxy; -   R₈₄ is hydrogen, halogen or C₁-C₄alkyl; -   U, V, W₁ and Z₄ are each independently of the others oxygen, sulfur,     C(R₉₂)R₉₃, carbonyl, NR₉₄, or a group -    wherein R₁₀₂ is C₂-C₄alkenyl or C₂-C₄alkynyl; with the provisos     that -   a) at least one of the ring members U, V, W₁ or Z₄ is carbonyl, and     a ring member adjacent to that ring member or to those ring members     is the group -    that group occurring only once; and -   b) two adjacent ring members U and V, V and W₁ and W₁ and Z₄ cannot     simultaneously be oxygen; -   R₉₅ and R₉₆ are each independently of the other hydrogen or     C₁-C₈alkyl; or -   R₉₅ and R₉₆ together form a C₂-C₆alkylene group; -   A₁ is R₉₉—Y₁— or —NR₉₇R₉₈; -   X₂ is oxygen or —S(O)₆; -   Y₁ is oxygen or sulfur; -   R₉₉ is hydrogen, C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₄alkoxy-C₁-C₈alkyl,     C₃-C₆alkenyloxy-C₁-C₈alkyl, or phenyl-C₁-C₈alkyl in which the phenyl     ring may be substituted by halogen, C₁-C₄alkyl, trifluoromethyl,     methoxy or by methyl-S(O)₅—, or is C₃-C₆alkenyl, C₃-C₆haloalkenyl,     phenyl-C₃-C₆alkenyl, C₃-C₆alkynyl, phenyl-C₃-C₆alkynyl, oxetanyl,     furyl or tetrahydrofuryl; -   R₈₅ is hydrogen or C₁-C₄alkyl; -   R₈₆ is hydrogen, C₁-C₄alkyl or C₁-C₄alkylcarbonyl; -   R₈₇ is hydrogen or C₁-C₄alkyl; or -   R₈₆ and R₈₇ together form a C₄- or C₅-alkylene group; -   R₈₈, R₈₉, R₉₀ and A₉₁ are each independently of the others hydrogen     or C₁-C₄alkyl; or R₈₈ together with R₈₉, or R₉₀ together with R₉₁,     are each independently of the other C₄- or C₅-alkylene in which one     carbon atom may have been replaced by oxygen or by sulfur, or one or     two carbon atoms may have been replaced by —NR₁₀₀—; -   R₉₂, R₁₀₀ and R₉₃ are each independently of the others hydrogen or     C₁-C₈alkyl; or -   R₉₂ and R₉₃ together are C₂-C₆alkylene; -   R₉₄ is hydrogen or C₁-C₈alkyl; -   R₉₇ is hydrogen, C₁-C₈alkyl, phenyl or phenyl-C₁-C₈alkyl, wherein     the phenyl rings may be substituted by fluorine, chlorine, bromine,     nitro, cyano, —OCH₃, C₁-C₄alkyl or by CH₃SO₂—, or is     C₁-C₄alkoxy-C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl; -   R₉₈ is hydrogen, C₁-C₈alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl; or -   R₉₇ and R₉₈ together are C₄- or C₅-alkylene in which one carbon atom     may have been replaced by oxygen or by sulfur, or one or two carbon     atoms may have been replaced by —NR₁₀₁—; -   R₁₀₁ is hydrogen or C₁-C₄alkyl; -   r is 0 or 1; and -   s is 0, 1 or 2, -   or of a compound of formula XVIII -    wherein R₁₀₃ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl     or C₃-C₆alkynyl; and R₁₀₄, R₁₀₅ and R₁₀₆ are each independently of     the others hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl or C₁-C₆alkoxy,     with the proviso that one of the substituents R₁₀₄, R₁₀₅ and R₁₀₆ is     other than hydrogen; -   or of a compound of formula XIX -    wherein Z₅ is N or CH, n is 0, 1, 2 or 3 when Z₅ is N, and n is 0,     1, 2, 3 or 4 when Z₅ is CH, R₁₀₇ is halogen, C₁-C₄alkyl,     C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, nitro, C₁-C₄alkylthio,     C₁-C₄alkylsulfonyl, C₁-C₄alkoxycarbonyl, phenyl or phenoxy, or     phenyl or phenoxy substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; -   R₁₀₈ is hydrogen or C₁-C₄alkyl, R₁₀₉ is hydrogen, C₁-C₄alkyl,     C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₄haloalkyl,     C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₁-C₄alkylthio-C₁-C₄alkyl,     C₁-C₄alkylsulfonyl-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl,     C₁-C₄alkenyloxy-C₁-C₄alkyl or C₁-C₄alkynyloxy-C₁-C₄alkyl; -   or of a compound of formula XX -    wherein Z₆ is oxygen or N—R₁₁₀ and R₁₁₀ is a group of formula -    wherein R₁₁₁ and R₁₁₂ are each independently of the other cyano,     hydrogen, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, aryl, phenyl or     heteroaryl, or phenyl, aryl or heteroaryl substituted by C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by     nitro; -   or of a compound of formula XXI -    wherein Z₇ is oxygen, sulfur, S═O, SO₂ or CH₂, R₁₁₃ and R₁₁₄ are     each independently of the other hydrogen, halogen or C₁-C₄alkyl, W₂     and W₃ are each independently of the other CH₂COOR₁₁₅ or COOR₀₁₁₅ or     together are a group of formula —(CH₂)C(O)—O—C(O)—(CH₂)—, and R₁₁₅     and R₀₁₁₅ are independently of the other hydrogen, C₁-C₄alkyl,     C₂-C₄alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, or a     metal cation or an ammonium cation; or of a compound of formula XXII -    wherein R₁₁₉ and R₁₂₀ are each independently of the other hydrogen,     halogen or C₁-C₄haloalkyl, R₁₂₁ is hydrogen, C₁-C₄alkyl,     C₃-C₄alkenyl, C₃-C₄alkynyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, a metal     cation or an ammonium cation, Z₈ is N, CH, C—F or C—Cl and W₄ is a     group of formula -    wherein R₁₂₂ and R₁₂₃ are each independently of the other hydrogen     or C₁-C₄alkyl and R₁₂₄ and R₁₂₅ are each independently of the other     hydrogen or C₁-C₄alkyl; or of a compound of formula XXIII -    wherein R₁₂₆ is hydrogen, cyano, halogen, C₁-C₄alkyl,     C₃-C₆cycloalkyl, C₁-C₄alkoxy, C₁-C₄alkoxycarbonyl,     C₁-C₄alkylthiocarbonyl, —NH—R₁₂₈, —C(O)NH—R₀₁₂₈, aryl or heteroaryl,     or aryl or heteroaryl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; -   R₁₂₇ is hydrogen, cyano, nitro, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl,     C₁-C₄alkoxy or C₁-C₄thioalkyl; and -   R₁₂₈ and R₀₁₂₈ are each independently of the other C₁-C₄alkyl,     C₁-C₄haloalkyl, C₃-C₄alkenyl, C₃-C₄alkynyl, C₃-C₄cycloalkyl, aryl or     heteroaryl, or aryl or heteroaryl substituted by C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by     nitro, formyl, C₁-C₄alkylcarbonyl or C₁-C₄alkylsufonyl; -   or of a compound of formula XXIV -    wherein R₁₂₉ and R₁₃₀ are each independently of the other hydrogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, mono-C₁-C₈- or     di-C₁-C₈alkylamino, C₃-C₆cycloalkyl, C₁-C₄thioalkyl phenyl or     heteroaryl, R₁₃₁ has the meanings of R₁₂₉ and in addition is OH,     NH₂, halogen, di-C₁-C₄aminoalkyl, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl     or C₁-C₄alkoxycarbonyl, R₁₃₂ has the meanings of R₁₂₉ and in     addition is cyano, nitro, carboxyl, C₁-C₄alkoxycarbonyl,     di-C₁-C₄aminoalkyl, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, SO₂—OH,     i-C₁-C₄aminoalkylsulfonyl or C₁-C₄alkoxysulfonyl, R₁₃₃ has the     meanings of R₁₂₉ and in addition is OH, NH₂, halogen,     di-C₁-C₄aminoalkyl, pyrrolidin-1-yl, piperidin-1-yl, morpholin-1-yl,     C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₁-C₄alkoxycarbonyl, phenoxy,     naphthoxy, phenylamino, benzoyloxy or phenylsulfonyloxy; -   or of a compound of formula XXV -    wherein R₁₃₄ is hydrogen, C₄alkyl, C₁-C₄haloalkyl, C₂-C₄alkenyl,     C₂-C₄alkynyl or C₁-C₄alkoxy-C₁-C₄alkyl, R₁₃₅ is hydrogen, halogen,     C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxy and R₁₃₆ is hydrogen,     halogen, C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxy, with the proviso     that R₁₃₅ and R₁₃₆ are not simultaneously hydrogen, or of formula     XXVI -    wherein -   R₁₄₃ is hydrogen, an alkali metal cation, alkaline earth metal     cation, sulfonium cation or ammonium cation or ethyl; -   or of formula XXVII -    wherein R₁₄₄ and R₁₄₅ are each independently of the other hydrogen,     C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl; -   R₁₄₆ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₆haloalkyl or     C₁-C₆haloalkoxy; -   R₁₄₇ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy,     C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl or nitro; -   n, is 0, 1, 2 or 3; and -   m is 1 or 2; -   or of formula XXVIII -    wherein -   R₁₄₈ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylthio,     C₃-C₈cycloalkyl, phenyl, phenyl-C₁-C₆alkyl or heteroaryl; wherein     the said groups may be substituted by halogen, cyano, nitro, amino,     hydroxy, carbonyl, carboxyl, formyl, carbonamide or by sulfonamide; -   R₁₄₉ is hydrogen, C₁-C₆alkyl or C₁-C₄haloalkyl; -   each R₁₅₀ is independently of any other(s) hydrogen, halogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,     C₁-C₄alkylsulfonyl, cyano, nitro, formyl or carboxyl; -   R₁₅₁ is hydrogen, C₁-C₆alkyl or C₁-C₄haloalkyl; -   each R₁₅₂ is independently of any other(s) hydrogen, halogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,     C₁-C₄alkylsulfonyl, cyano, nitro, formyl or carboxyl; -   o is 0, 1, or 2, and -   p is 0, 1 or 2; -   or of formula XXIX -    wherein -   R₁₅₉ is hydrogen, formyl, C₁₋₆alkylcarbonyl, C₁₋₆alkenylcarbonyl,     C₁₋₆alkynylcarbonyl, C₁₋₆alkoxycarbonyl, C₁₋₆alkylthiocarbonyl,     C₃₋₈cycloalkylcarbonyl, phenyl-C₁₋₆alkylcarbonyl, phenylcarbonyl,     C₁₋₆alkylsulfonyl, C₁₋₆alkenylsulfonyl or phenylsultonyl, wherein     the aforementioned hydrocarbon groups may be substituted by one or     more halogen atoms, cyano, nitro, amino, methoxy, ethoxy or phenyl; -   R₁₅₃ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl,     C₃₋₈cycloalkyl, formyl, C₁₋₆alkylcarbonyl, C₁₋₆alkenylcarbonyl,     C₁₋₆alkynylcarbonyl, C₁₋₆alkoxycarbonyl, C₁₋₆alkylthiocarbonyl,     C₃₋₈cycloalkylcarbonyl, C₁₋₆alkylsulfonyl, C₁₋₆alkenylsulfonyl or     phenylsulfonyl, wherein the aforementioned hydrocarbon groups may be     substituted by one or more halogen atoms, cyano, nitro, amino,     methoxy, ethoxy or phenyl; -   R₁₅₄ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl,     C₃₋₈cycloalkyl, formyl, C₁₋₆alkylcarbonyl, C₁₋₆alkenylcarbonyl,     C₁₋₆alkynylcarbonyl, C₁₋₆alkoxycarbonyl, C₁₋₆alkylthiocarbonyl,     C₃₋₈cycloalkylcarbonyl, C₁₋₆alkylsulfonyl, C₁₋₆alkenylsulfonyl or     phenylsulfonyl, wherein the afore-mentioned hydrocarbon groups may     be substituted by one or more halogen atoms, cyano, nitro, amino,     methoxy, ethoxy or phenyl; -   R₁₅₅, R₁₅₆, R₁₅₇, and R₁₅₈ are each independently of the others     hydrogen, halogen, amino, C₁₋₃alkylamino, C₁₋₆dialkylamino, hydroxy,     cyano, nitro, formyl, carboxyl, C₁₋₆alkoxy, C₁₋₆haloalkoxy,     C₁₋₆alkylcarbonyl, C₁₋₆alkoxycarboxyl, C₁₋₆alkyl, C₁₋₆haloalkyl,     C₁₋₆alkenyl or C₁₋₆alkynyl; -   or R₁₅₃ and R₁₅₈, together with the ring atoms to which they are     bonded, form a five- or six-membered, partially saturated or     unsaturated ring that may contain up to 2 identical or different     hetero atoms from the group oxygen, sulfur and nitrogen, it being     possible for that ring to be substituted by an oxo radical.

Preferably, the compositions according to the invention comprise a herbicide-antagonistically effective amount of a safener of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV or XXV.

Preferably, the selective-herbicidal composition according to the invention comprises, in herbicide-antagonistically effective amount, either a compound of formula X

-   wherein R₃₇ is hydrogen, C₁-C₈alkyl, or C₁-C₈alkyl substituted by     C₁-C₆alkoxy or by C₃-C₆alkenyloxy; and X₆ is hydrogen or chlorine;     or a compound of formula XI     wherein -   E is nitrogen or methine; R₃₈ is —CCl₃, phenyl, or phenyl     substituted by halogen; -   R₃₉ and R₄₀ are each independently of the other hydrogen or halogen;     and -   R₄₁ is C₁-C₄alkyl; or a compound of formula XII -    wherein R₄₄ and R₄₅ are each independently of the other hydrogen or     halogen, and R₄₆ R₄₇ and R₄₈ are each independently of the others     C₁C₄alkyl.

The above-mentioned preferences of the compounds of formula I apply also in mixtures of compounds of formula I with the safeners of formulae X to XVIII. Preferred compositions according to the invention comprise a safener selected from the group of formula Xa

formula Xb

and formula XIa

Further preferred compounds of formulae X, XI and XII are also listed in Tables 9, 10 and 11.

TABLE 9 Compounds of formula X: (X)

Comp. No. X₆ R₃₇ 9.01 Cl —CH(CH₃)—C₅H₁₁-n 9.02 Cl —CH(CH₃)—CH₂OCH₂CH═CH₂ 9.03 Cl H 9.04 Cl C₄H₉-n

Preferred compounds of formula XI are listed in the following Table 10.

TABLE 10 Compounds of formula XI: (XI)

Comp. No. R₄₁ R₃₈ R₃₉ R₄₀ E 10.01 CH₃ phenyl 2-Cl H CH 10.02 CH₃ phenyl 2-Cl 4-Cl CH 10.03 CH₃ phenyl 2-F H CH 10.04 CH₃ 2-chlorophenyl 2-F H CH 10.05 C₂H₅ CCl₃ 2-Cl 4-Cl N 10.06 CH₃ phenyl 2-Cl 4-CF₃ N 10.07 CH₃ phenyl 2-Cl 4-CF₃ N

Preferred compounds of formula XII are listed in the following Table 11.

TABLE 11 Compounds of formula XII: (XII)

Comp. No. R₄₅ R₄₇ R₄₈ R₄₄ R₄₅ 11.01 CH₃ CH₃ CH₃ 2-Cl 4-Cl 11.02 CH₃ C₂H₅ CH₃ 2-Cl 4-Cl 11.03 CH₃ C₂H₅ C₂H₅ 2-Cl 4-Cl

Preferred compounds of formula XII are listed in the following Table 12 as compounds of formula XIIIa:

TABLE 12 Compounds of formula XIIIa: (XIIIa)

Comp. No. A₂ R₅₁ 12.001

H 12.002

H 12.003

CH₃ 12.004

CH₃

Preferred compounds of formula XIV are listed in the following Table 13:

TABLE 13 Compounds of formua XIV: (XIV)

Comp. No. R₅₀ R₅₇ R₅₆ + R₅₇ 13.001 CH═CHCH₂ CH═CHCH₂ — 13.002 — —

13.003 — —

13.004 — —

13.005 — —

13.006 — —

13.007 — —

13.008 — —

Preferred compounds of formula XV are listed in the following Table 14:

TABLE 14 Compounds of formula XV: (XV)

Comp. No R₈₀ R₇₉ 14.01 H CN 14.02 Cl CF₃

Preferred compounds of formula XVI are listed in the following Table 15:

TABLE 15 Compounds of formula XVI: (XVI)

Comp. No. R₈₁ 15.01 H 15.02 CH₃

Preferred compounds of formula XVII are listed in the following Table 16 as compounds of formula XVIIa:

TABLE 16 Compounds of formula XVIIa (XVIIa)

Comp. No. R₈₂ Z₄ V r 16.001 H

O 1 16.002 H

O 1 16.003 H

O 1 16.004 H

O 1 16.005 H

CH₂ 1 16.006 H

CH₂ 1 16.007 H

S 1 16.008 H

S 1 16.009 H

NCH₃ 1 16.010 H

NCH₃ 1 16.011 H

NCH₃ 1 16.012 H

O 1 16.013 H

S 1

Preferred compounds of formula XVII are listed in the following Table 17 as compounds of formula XVIIb:

TABLE 17 Compounds of formula XVIIb (XVIIb)

Comp. No. U R₈₂ Z₄ 17.001 O H

17.002 O H

17.003 O 5-Cl

17.004 CH₂ H

17.005 CH₂ H

17.006 CH₂ H

17.007 NH 5-Cl

17.008 NH 5-Cl

17.009 NH H

17.010 NH H

17.011 NCH₃ H

17.012 NCH₃ H

Preferred compounds of formula XVII are listed in the following Table 18 as compounds of formula XVIIc:

TABLE 18 Compounds of formula XVIIc (XVIIc)

Comp. No. U V R W₁ Z₄ R₈₂ 18.001 O C═O 1

CH₂ H 18.002 O C═O 1

CH₂ H 18.003 CH₂ C═O 1

CH₂ H 18.004 CH₂ C═O 1

CH₂ H 18.005 CH₂ CH₂ 1

C═O H 18.006 CH₂ CH₂ 1

C═O H 18.0007 NCH₃ C═O 1

CH₂ H

Preferred compounds of formula XVII are listed in the following Table 19 as compounds of formula XVIId:

TABLE 19 Compounds of formula XVIId (XVIId)

Comp. No. R₈₂ W₁ 19.001 6-Cl

19.002 6-Cl

19.003 H

19.004 H

19.005 H

Preferred compounds of formula XVIII are listed in the following Table 20:

TABLE 20 Compounds of formula XVIII (XVIII)

Comp. No. R₁₀₃ R₁₀₄ R₁₀₅ R₁₀₆ 20.01 CH₃ H cyclopropyl H 20.02 CH₃ C₂H₅ cyclopropyl H 20.03 CH₃ cyclopropyl C₂H₅ H 20.04 CH₃ CH₃ H H 20.05 CH₃ CH₃ cyclopropyl H 20.06 CH₃ OCH₃ OCH₃ H 20.07 CH₃ CH₃ OCH₃ H 20.08 CH₃ OCH₃ CH₃ H 20.09 CH₃ CH₃ CH₃ H 20.10 C₂H₅ CH₃ CH₃ H 20.11 C₂H₅ OCH₃ OCH₃ H 20.12 H OCH₃ OCH₃ H 20.13 H CH₃ CH₃ H 20.14 C₂H₅ H H CH₃ 20.15 H H H CH₃ 20.16 CH₃ H H CH₃ 20.17 CH₃ CH₃ H CH₃

Of the compounds of formula XXVIII, preference is given to those wherein

-   R₁₄₈ is hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkyl or phenyl, wherein the     said groups may be substituted by halogen, cyano, nitro, amino,     hydroxy, carbonyl, carboxyl, formyl, carbon-amide or sulfonamide; -   R₁₄₉ is hydrogen; -   each R₁₅₀ is independently of any other(s) hydrogen, halogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, cyano,     nitro or formyl -   R₁₅₁, is hydrogen; and -   each R₁₅₂ is independently of any other(s) hydrogen, halogen,     C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, cyano,     nitro or formyl.

Especially preferred compounds of formula XXVIII are selected from the group

-   2-methoxy-N-[4-(2-methoxybenzoylsulfamoyl)phenyl]-acetamide, -   N-[4-(2-methoxybenzoylsulfamoyl)phenyl]-cyclopropanecarboxamide, -   N-[4-(2-methoxybenzoylsulfamoyl)phenyl]-cyclobutanecarboxamide, -   N-[4-(2-chlorobenzoylsulfamoyl)phenyl]-cyclopropanecarboxamide, -   N-[4-(2-chlorobenzoylsulfamoyl)phenyl]-acetamide, -   N-[4-(2-trifluoromethoxybenzoylsulfamoyl)phenyl]-acetamide, -   N-[4-(2-trifluoromethylbenzoylsulfamoyl)phenyl]-cyclopropanecarboxamide, -   N-[4-(2-trifluoromethoxybenzoylsultamoyl)phenyl]-cyclopropanecarboxamide, -   N-[4-(2-trifluoromethoxybenzoyisulfamoyl)phenyl]-cyclobutanecarboxamide     and -   N-[4-(2-trifluoromethylbenzoylsulfamoyl)phenyl]-acetamide.

Of the compounds of formula XXIX, preference is given to those wherein

-   R₁₅₉ is hydrogen, formyl, C₁₋₆alkylcarbonyl, C₁₋₆alkenylcarbonyl,     C₁₋₆alkynylcarbonyl, C₁₋₆alkoxycarbonyl, C₁₋₆alkylthiocarbonyl,     C₃₋₈cycloalkylcarbonyl, phenyl-C₁₋₆alkylcarbonyl or phenylcarbonyl,     wherein the afore-mentioned hydrocarbon radicals may be substituted     by one or more halogen atoms, cyano, nitro, amino, methoxy, ethoxy     or phenyl; -   R₁₅₃ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl, formyl,     C₁₋₆alkylcarbonyl or C₁₋₆alkoxy-carbonyl, wherein the     afore-mentioned hydrocarbon radicals may be substituted by one or     more halogen atoms, cyano, nitro, amino, methoxy, ethoxy or phenyl; -   R₁₅₄ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl, formyl,     C₁₋₆alkylcarbonyl or C₁₋₈alkoxy-carbonyl, wherein the     afore-mentioned hydrocarbon radicals may be substituted by one or     more halogen atoms, cyano, nitro, amino, methoxy, ethoxy or phenyl; -   R₁₅₅, R₁₅₆, R₁₅₇ and R₁₅₈ are each independently of the others     hydrogen, halogen, cyano, nitro, formyl, carboxyl, C₁₋₆alkoxy,     C₁₋₆haloalkoxy, C₁₋₆alkylcarbonyl, C₁₋₆alkoxycarboxyl, C₁₋₆alkyl or     C₁₋₆haloalkyl; -   or R₁₅₃ and R₁₅₈, together with the ring atoms to which they are     bonded, form a five- or six-membered, partially saturated or     unsaturated ring that may contain up to 2 identical or different     hetero atoms from the group oxygen, sulfur and nitrogen, it being     possible for that ring to be substituted by an oxo radical.

Special preference is given to compounds of formula XXIX wherein

-   R₁₅₉ is hydrogen, formyl, C₁₋₆alkylcarbonyl, C₁₋₆alkenylcarbonyl,     C₁₋₆alkynylcarbonyl, C₁₋₆alkoxycarbonyl, C₁₋₈alkylthiocarbonyl,     C₃₋₈cycloalkylcarbonyl or phenylcarbonyl; -   R₁₅₃ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl, formyl,     C₁₋₆alkylcarbonyl or C₁₋₆alkoxy-carbonyl; -   R₁₅₄ is hydrogen, C₁₋₆alkyl, C₁₋₆alkenyl, C₁₋₆alkynyl, formyl,     C₁₋₆alkylcarbonyl or C₁₋₆alkoxy-carbonyl; -   R₁₅₅, R₁₅₆, R₁₅₇, and R₁₅₈ are each independently of the others     hydrogen, halogen, cyano, nitro, formyl, C₁₋₆alkyl, C₁₋₆haloalkyl,     C₁₋₆alkoxy or C₁₋₆haloalkoxy; -   or R₁₅₃ and R₁₅₈, together with the ring atoms to which they are     bonded, form a five- or six-membered, partially saturated or     unsaturated ring that may contain up to 2 identical or different     hetero atoms from the group oxygen, sulfur and nitrogen, it being     possible for that ring to be substituted by an oxo radical.

Very special preference is given to compounds of formula XXIX selected from the group

-   4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   1-ethyl-4-hydroxy-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   6-hydroxy-5-(1H-tetrazole-5-carbonyl)-1,2-dihydro-pyrrolo[3.2.1-.ij.]quinolin-4-one, -   3-(1-acetyl-1H-tetrazole-5-carbonyl)-4-hydroxy-1-methyl-1H-quinolin-2-one, -   6-chloro-4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   6-fluoro-4-hydroxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   4-hydroxy-1,6-dimethyl-3-(1H-tetrazole-5carbonyl)-1H-quinolin-2-one, -   4-hydroxy-6-methoxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   4-hydroxy-6-methoxy-1-methyl-3-(1H-tetrazole-5-carbonyl)-1H-quinolin-2-one, -   acetic acid     1-methyl-2-oxo-3-(1H-tetrazole-5-carbonyl)-1,2-dihydro-quinolin-4-yl     ester and -   2,2-dimethylpropionic acid     1-methyl-2-oxo-3-(1H-tetrazole-5-carbonyl)-1,2-dihydroquinolin-4-yl     ester.

The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, the seeds or cuttings thereof or the area of cultivation thereof simultaneously or separately with a herbicidally effective amount of a herbicide of formula I and a herbicide-antagonistically effective amount of a safener of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, preferably of formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII.

Suitable cultivated plants that can be protected against the harmful effect of the above-mentioned herbicides by the safeners of formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII are especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, more especially maize and cereals. Crops are also to be understood as including those that have been rendered tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods.

The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, for example the monocotyledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitara, Brachiaria, Echinochloa, Panicum, Sorghum hal./bic., Rottboellia, Cyperus, Brachiaria, Echinochloa, Scirpus, Monochoria, Sagittaria and Stellaria and the dicotyledenous weeds Sinapis, Chenopodium, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.

Areas of cultivation are areas of land on which the cultivated plants are already growing or in which the seeds of those cultivated plants have already been sown, as well as the areas of land on which it is intended to grow those cultivated plants.

A safener of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX may, depending on the intended purpose, be used to pretreat the seed material of the cultivated plant (dressing the seed or the cuttings) or may be incorporated into the soil before or after sowing. It can, however, also be applied alone or together with the herbicide after the emergence of the plants. The treatment of the plants or seed with the safener can therefore, in principle, be effected independently of the time at which the herbicide is applied. The treatment of the plants can, however, also be carried out by applying the herbicide and safener simultaneously (for example in the form of a tank mixture). The rate of application of the safener in relation to the herbicide depends largely on the method of application. In the case of field treatment, which is effected either using a tank mixture comprising a combination of safener and herbicide or by the separate application of safener and herbicide, the ratio of herbicide to safener is generally from 100:1 to 1:10, preferably from 20:1 to 1:1. In the case of field treatment, from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha, is generally applied.

The rate of application of herbicide is generally from 0.001 to 2 kg/ha, but is preferably from 0.005 to 0.5 kg/ha.

The compositions according to the invention are suitable for any of the methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing.

In the case of seed dressing, from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, is generally applied. When the safener is applied in liquid form shortly before sowing, with swelling of the seed, it is advantageous to use safener solutions that comprise the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.

For application, the safeners of formula X, XI, XII, XII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, or combinations of those safeners with the herbicides of formula I, are advantageously processed, together with the adjuvants customary in formulation technology, into formulations, for example into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.

Such formulations are described, for example, in WO 97134485, on pages 9 to 13. The formulations are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, for example solvents or solid carriers. Furthermore, in addition surface-active compounds (surfactants) can be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485, on page 6.

Depending on the nature of the active ingredient of formula I to be formulated, there come into consideration as surface-active compounds non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifiying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of active ingredient mixture comprising the compound of formula I and the compounds of formulae X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, from 1 to 99.9% by weight of a solid or liquid formulation adjuvant and from Q to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will usually preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further additives, such as stabilisers, vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers and also fertilisers or other active ingredients. There are various suitable methods and techniques for using safeners of formulae X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX or compositions comprising them to protect cultivated plants against the harmful effects of herbicides of formula I; the following are examples:

i) Seed Dressing

a) Dressing the seeds with a wettable powder formulation of an active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, by shaking in a vessel until the formulation is uniformly distributed on the seed surface (dry dressing). Approximately from 1 to 500 g of active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed.

b) Dressing the seeds with an emulsifiable concentrate of an active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX in accordance with method a) (wet dressing).

c) Dressing by immersing the seeds in a liquid formulation containing from 100 to 1000 ppm of active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX for from 1 to 72 hours and, if desired, subsequently drying the seeds (immersion dressing).

Dressing the seeds or treating the germinated seedlings are naturally the preferred methods of application, because treatment with the active ingredient is directed wholly at the target crop. From 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, is generally used per 100 kg of seed, although depending on the method employed, which also allows the addition of other active ingredients or micronutrients, amounts that exceed or fall short of the specified concentration limits may be employed (repeat dressing).

ii) Application in the Form of a Tank Mixture

A liquid formulation of a mixture of antidote and herbicide (ratio of the one to the other from 10:1 to 1:100) is used, the rate of application of herbicide being from 0.005 to 5.0 kg per hectare. Such tank mixtures are applied before or after sowing.

iii) Application to the Seed Furrow

The active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. After the seed furrow has been covered, the herbicide is applied pre-emergence in the normal manner.

iv) Controlled Active Ingredient Release

The active ingredient of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX is applied in solution to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. Where appropriate, it is also possible to apply a coating (coated granules) that allows the active ingredient to be released in metered amounts over a specific period.

The activity of herbicidal and plant growth-inhibiting compositions according to the invention comprising a herbicidally effective amount of compound of formula I and a herbicide-antagonistically effective amount of compound of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX can be increased by the addition of spray tank adjuvants.

Such adjuvants may be, for example: non-ionic surfactants, mixtures of non-ionic surfactants, mixtures of anionic surfactants with non-ionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with and without surfactants, vegetable oil derivatives with and without the addition of surfactant, alkylated derivatives of oils of vegetable or mineral origin with and without surfactants, fish oils and other animal oils of animal nature and alkyl derivatives thereof with and without surfactants, naturally occurring higher fatty acids, preferably having from 8 to 28 carbon atoms, and alkyl ester derivatives thereof, organic acids containing an aromatic ring system and one or more carboxylic acid esters, and alkyl derivatives thereof, and also suspensions of polymers of vinyl acetate or copolymers of vinyl acetate/acrylic acid esters. Mixtures of individual adjuvants with one another and combined with organic solvents may lead to the activity being further increased.

Suitable non-ionic surfactants include, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and alkylphenols, preferably that can contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and from 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts of polypropylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having preferably from 1 to 10 carbon atoms in the alkyl chain, which adducts contain preferably from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups. The said compounds usually contain from 1 to 5 ethylene glycol units per propylene glycol unit.

There may also be mentioned, as further examples of non-ionic surfactants, nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxy ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylenesorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable.

Preferred anionic surfactants are especially alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids, and ethoxylated derivatives thereof. The alkyl radicals usually contain from 8 to 24 carbon atoms.

Preferred non-ionic surfactants are known by the following trade names:

polyoxyethylene cocoalkylamine (e.g. AMIET® 105 (Kao Co.)), polyoxyethylene oleylamine (e.g. AMIET® 415 (Kao Co.)), nonylphenol polyethoxyethanols, polyoxyethylene stearylamine (e.g. AMIET® 320 (Kao Co.)), N-polyethoxyethylamines (e.g. GENAMIN® (Hoechst AG)), N,N,N′,N′-tetra(polyethoxypolypropoxyethyl)ethylene-diamine (e.g. TERRONIL® and TETRONIC® (BASF Wyandotte Corp.)), BRIJ® (Atlas Chemicals), ETHYLAN® CD and ETHYLAN® D (Diamond Shamrock), GENAPOL® C, GENAPOL® O, GENAPOL® S and GENAPOL® X080 (Hoechst AG), EMULGEN® 104P, EMULGEN® 109P and EMULGEN® 408 (Kao Co.); DISTY® 125 (Geronazzo), SOPROPHOR® CY 18 (Rhone Poulenc S.A.); NONISOL® (Ciba-Geigy), MRYJ® (ICI); TWEEN® (ICI); EMULSOGEN® (Hoechst AG); AMIDOX® (Stephan Chemical Co.), ETHOMID® (Armak Co.); PLURONIC® (BASF Wyandotte Corp.), SOPROPHOR® 461 P (Rh{circumflex over (0)}ne Poulenc S.A.), SOPROPHOR® 496/P (Rhone Poulenc S.A.), ANTAROX FM63 (Rhone Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (Osi-Specialities).

The cationic surfactants are especially quaternary ammonium salts that contain as N-substituent(s) at least one alkyl radical having from 8 to 22 carbon atoms and, as further substituents, optionally halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The oils used are either of mineral or natural origin. The natural oils can in addition be of animal or vegetable origin. Of the animal oils preference is given especially to derivatives of beef tallow, but fish oils (e.g. sardine oil) and derivatives thereof are also used. Vegetable oils are mostly seed oils of varied origin. Examples of vegetable oils used especially that may be mentioned include coconut oil, rapeseed oil and sunflower oil and derivatives thereof.

In the composition according to the invention, the concentrations of oil additive are generally from 0.01 to 2% based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.

Preferred oil additives in the composition according to the invention comprise an oil of vegetable origin, for example rapeseed oil or sunflower oil, alkyl esters of oils of vegetable origin, for example methyl derivatives, or mineral oils.

Especially preferred oil additives comprise alkyl esters of higher fatty acids (C₈-C₂₂), especially methyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).

The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.

Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland).

The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30% by weight.

Examples of oil additives that consist of mixtures of oils or mineral oils, or derivatives thereof, with surfactants include Edenor ME SU®, Emery 2231® (Henkel subsidiary Cognis GMBH, DE), Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) or, more especially, Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can also bring about further increase in activity. Suitable solvents include, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types.

The concentration of such solvents can be from 10 to 80%, by weight, of the total weight.

Such oil additives, which, for example, are also described in U.S. Pat. No. 4,834,908, are especially preferred for the composition according to the invention. A more especially preferred oil additive is known by the name MERGE®, can be obtained from BASF Corporation and is basically described, for example, in U.S. Pat. No. 4,834,908, col. 5, as Example COC-1. A further oil additive that is preferred in accordance with the invention is SCORE® (Novartis Crop Protection Canada).

Surfactants, oils, especially vegetable oils, derivatives thereof, such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants, such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and also higher fatty acids, that are customary in formulation and adjuvant technology and that can also be used in the compositions according to the invention and in spray tank solutions thereof, are described, inter alia, in “McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1998, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, “A Compendium of Herbicide Adjuvants”. Southern Illinois Univ., 1998, L. Thomson Harvey, “A Guide to Agricultural Spray Adjuvants Used in the United States”, Thomson Pubns., 1992.

Preferred formulations have especially the following compositions (%=percent by weight)

Emulsifiable Concentrates:

-   active ingredient mixture: from 1 to 90%, preferably from 5 to 20% -   surface-active agent: from 1 to 30%, preferably from 10 to 20% -   liquid carrier: from 5 to 94%, preferably from 70 to 85%     Dusts: -   active ingredient mixture: from 0.1 to 10%, preferably from 0.1 to     5% -   solid carrier: from 99.9 to 90%, preferably from 99.9 to 99%     Suspension Concentrates: -   active ingredient mixture: from 5 to 75%, preferably from 10 to 50% -   water: from 94 to 24%, preferably from 88 to 30% -   surface-active agent: from 1 to 40%, preferably from 2 to 30%     Wettable Powders: -   active ingredient mixture: from 0.5 to 90%, preferably from 1 to 80% -   surface-active agent: from 0.5 to 20%, preferably from 1 to 15% -   solid carrier: from 5 to 95%, preferably from 15 to 90%     Granules: -   active ingredient mixture: from 0.1 to 30%, preferably from 0.1 to     15% -   solid carrier: from 99.5 to 70%, preferably from 97 to 85%

The Examples that follow illustrate the invention further. They do not limit the invention.

Formulation Examples for mixtures of herbicides of formula I and safener of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX (%=percent by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture  5% 10% 25% 50% calcium dodecylbenzenesulfonate  6%  8%  6%  8% castor oil polyglycol ether  4% —  4%  4% (36 mol of ethylene oxide) octylphenol polyglycol ether —  4% —  2% (7-8 mol of ethylene oxide) cyclohexanone — — 10% 20% aromatic C₉-C₁₂hydrocarbon mixture 85% 78% 55% 16%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient mixture  5% 10% 50% 90% 1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycol (mol. wt. 400) 20% 10% — — N-methyl-2-pyrrolidone — — 30% 10% aromatic C₉-C₁₂hydrocarbon mixture 75% 60% — —

The solutions are suitable for application in the form of micro-drops.

F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% —  3% — sodium lauryl sulfate 2%  3% —  4% sodium diisobutylnaphthalenesulfonate —  6%  5%  6% octylphenol polyglycol ether —  1%  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 1%  3%  5% 10% kaolin 88%  62% 35% —

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient mixture  0.1%  5% 15% highly dispersed silicic acid  0.9%  2%  2% inorganic carrier material 99.0% 93% 83% ( 0.1-1 mm) for example CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

F5. Coated granules a) b) c) active ingredient mixture 0.1% 5% 15% polyethylene glycol (mol. wt. 200) 1.0% 2%  3% highly dispersed silicic acid 0.9% 1%  2% inorganic corner material 98.0%  92%  80% ( 0.1-1 mm) for example CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier material moistened with polyethylene glycol, yielding non-dusty coated granules.

F6. Extruder granules a) b) c) d) active ingredient mixture 0.1% 3% 5% 15% sodium lignosulfonate 1.5% 2% 3% 4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 97.0%  93%  90%  79% 

The active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and then dried in a stream of air.

F7. Dusts a) b) c) active ingredient mixture  0.1%  1%  5% talcum 39.9% 49% 35% kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether — 1% 2% — (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde solution 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

It is often more practical to formulate the active ingredient of formula I and the mixing partner of formula X, XI, XII, XII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX separately and then, shortly before application, to bring them together in the applicator in the desired mixing ratio in the form of a “tank mixture” in water.

The ability of the safeners of formula X, XI, XII, XII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX to protect cultivated plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples.

BIOLOGICAL EXAMPLE 1 Safening Action

Under greenhouse conditions, the test plants are grown in plastics pots to the 4-leaf stage. At that stage, on the one hand the herbicide alone, and on the other hand mixtures of the herbicide with the test substances to be tested as safeners, are applied to the test plants. The test substances are applied in the form of an aqueous suspension prepared from a 25% wettable powder (Example F3, b)), using 500 liters of water/ha. 2 to 3 weeks after application, the phytotoxic action of the herbicide on the cultivated plants, for example maize and cereals, is evaluated using a percentage scale. 100% indicates that the test plant has died, and 0% indicates no phytotoxic action.

The results obtained in this test demonstrate that the damage caused to the cultivated plant by the herbicide of formula I can be appreciably reduced by the compounds of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX. Examples of those results are given in the following Table B5:

TABLE B5 Post-emergence action of a mixture according to the invention of herbicide and safener: Comp. No. 1.01 (60 g/ha) + Test plant Comp. No. 1.01 (60 g/ha) Comp. No. 11.03 (15 g/ha) Barley 20  0 Agrostis 70 70 Alopecurus 70 80 Lolium 70 70

It can be seen from Table 5 that compound No. 1.01 exhibits a phytotoxic effect of 20% on barley, which is not tolerable. The weeds Agrostis, Alopecurus und Lolium are satisfactorily controlled.

In contrast, the mixture according to the invention, consisting of herbicide No. 1.01 and safener No. 11.03, has no phytotoxic effect on the cultivated plant. At the same time, the herbicidal effect on the weeds is not only identical but surprisingly, in the case of Alopecurus, even increased (80% compared with the 70% achieved with the application of herbicide No. 1.01 on its own).

The same results are obtained when the mixtures are formulated in accordance with Examples F1, F2 and F4 to F8.

The compound of formula I can advantageously be mixed with a number of other known herbicides. As a result, for example, the spectrum of weeds is substantially broadened and in many cases an increase in selectivity with respect to the useful plants is achieved. In particular, mixtures of the compound of formula I with at least one of the following herbicides are important:

-   herbicides from the class of the phenoxy-phenoxypropionic acids, for     example diclofop-methyl, fluazifop-P-butyl, quizalafop-P-ethyl,     propaquizafop, clodinafop-P-propargyl, cyhalfop-butyl,     fenoxaprop-P-ethyl, haloxyfop-methyl or haloxyfop-etoethyl; -   herbicides from the class of the hydroxylamines, for example     sethoxidim, alloxydim, clethodim, cycloxydim, tepralkoxydim,     tralkoxydim or butroxidim; -   herbicides from the class of the sulfonylureas, for example     amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl,     cinosulfuron, chlorsulfuron, chlorimuron, cyclosulfamuron,     ethametsulfuron-methyl, ethoxysulfuron, fluazasulfuron,     flupyrsulfuron, imazosulfuron, iodosulfuron (CAS RN 144550-36-7 and     185119-76-0), metsulfuron-methyl, nicosulfuron, oxasulfuron,     primisulfuron, pyrazosulfuron-ethyl, sulfosulfuron, rimsulfuron,     thifensulfuron-methyl, triasulfuron, tribenuron-methyl,     triflusulfuron-methyl, prosulfuron, flucarbazone or tritosulfuron     (CAS RN 142469-14-5); -   herbicides from the class of the imidazolinones, such as     imazethapyr, imazamethabenz, imazamethapyr, imazaquin, imazamox or     imazapyr; -   herbicides from the class of the pyrimidines, such as     pyrithiobac-sodium, pyriminobac, bispyribac-sodium; -   herbicides from the class of the triazines, for example atrazine,     simazine, simethryne, terbutryne, terbuthylazine; -   herbicides from the class of the ureas, such as isoproturon,     chlortoluron, diuron, dymron, fluometuron, linuron or     methabenzthiazuron; -   herbicides from the class of the phosphonic acid derivatives, for     example glyphosate, glufosinate, sulfosate or phosphinothricin; -   herbicides from the class of the PPO, for example nitrofen, bifenox,     acifluorfen, lactofen, oxyfluorfen, ethoxyfen, fluoroglycofen,     fomesafen, halosafen, azafenidin (CAS RN.-68049-83-2), benzfendizone     (CAS RN 158755-954), butafenacil (known from U.S. Pat. No.     5,183,492, CAS RN 158755-95-4), carfentrazone-ethyl, cinidon-ethyl     (CAS RN 142891-20-1), flumichlorac-pentyl, flumioxazin,     fluthiacet-methyl, oxadiargyl, oxadiazon, pentoxazone,     sulfentrazone, fluazolate (CAS RN 174514-07-9) or pyraflufen-ethyl; -   herbicides from the class of the chloroacetanilides, for example     alachlor, acetochlor, butachlor, dimethachlor, dimethenamid,     S-dimethenamid, metazachlor, metolachlor, S-metolachlor,     pretilachlor, propachlor, propisochlor, thenylchlor or pethoamid     (CASRN 106700-29-2) -   herbicides from the class of the phenoxyacetic acids, for example     2,4-D, fluroxypyr, MCPA, MCPP, MCPB, trichlorpyr or mecropop-P; -   herbicides from the class of the triazinones, for example     hexazinone, metamitron or metribuzin; -   herbicides from the class of the dinitroanilines, for example     oryzalin, pendimethalin or trifluralin; -   herbicides from the class of the azinones, for example chloridazon     or norflurazon; -   herbicides from the class of the carbamates, for example     chlorpropham, desmedipham, phenmedipham or propham; -   herbicides from the class of the oxyacetamides, for example     mefenacet or fluthiacet; -   herbicides from the class of the thiolcarbamates, for example     butylate, cycloate, diallate, EPTC, esprocarb, molinate,     prosulfocarb, thiobencarb or triallate; -   herbicides from the class of the azoloureas, for example     fentrazamide (CAS RN158237-07-1) or cafenstrole; -   herbicides from the class of the benzoic acids, for example dicamba     or picloram; -   herbicides from the class of the anilides, for example diflufenican,     or propanil; -   herbicides from the class of the nitrites, for example bromoxynil,     dichlobenil or ioxynil; -   herbicides from the class of the triones, for example sulcotrione,     mesotrione (known from U.S. Pat. No. 5,006,158), isoxaflutole or     isoxachlortole; -   herbicides from the class of the sulfonamides, for example     flucarbazone (CAS RN 181274-17-9), procarbazone (CAS RN     145026-81-9), chlorasulam, diclosulam (CAS RN 145701-21-9),     florasulam, flumetsulam or metosulam; -   and also amitrole, benfuresate, bentazone, cinmethylin, clomazone,     chlopyralid, difenzoquat, dithiopyr, ethofumesate, flurochloridone,     indanofan, isoxaben, oxaziclomefone, pyridate, pyridafol (CAS RN.     40020-01-7), quinchlorac, quinmerac, tridiphane or flamprop.

Unless specificed otherwise, the above-mentioned mixing partners of the compound of formula I are known from The Pesticide Manual, Eleventh Edition, 1997, BCPC. The mixing partners of the compound of formula I can, if desired, also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

The following Examples illustrate the invention further without implying any limitation.

PREPARATION EXAMPLES Example P1 Preparation of

To a solution of 20 g of 2-(2,6-dibromo-4-methyl-phenyl)-malonic acid dimethyl ester (52.6 mmol) in 400 ml of toluene (degassed 3 times, vacuum/argon) there are added first 36.7 g (0.116 mol) of tributylvinylstannane and then 2 g of tetrakis(triphenylphosphine)-palladium. The reaction mixture is then stirred for 9 hours at a temperature of from 90 to 95° C. After filtration over Hyflo and concentration using a rotary evaporator, and after purification by chromatography, 15.3 g of (8) are obtained in the form of a yellow oil, which is used in the next reaction without being further purified.

Example P2

15.2 g of compound (8) obtained according to Example P1 are hydrogenated with hydrogen over a palladium catalyst (carbon as carrier, 7 g of 5% Pd/C) in 160 ml of tetrahydrofuran at a temperature of from 20 to 250° C. When the hydrogenation is complete, the product is filtered over Hyflo and the filtrate obtained is concentrated using a rotary evaporator. 13.7 g of (9) are obtained in the form of yellow crystals having a melting point of from 47 to 49° C.

Example P3

71.8 g (0.71 mol) of triethylamine are added to a suspension of 40 g (0.15 mol) of (4) in 1000 ml of xylene and the mixture is degassed (4 times, vacuum/argon). The yellow suspension is then heated to a temperature of 60° C. and stirred for 3 hours. 42.5 g (0.15 mol) of (5) are subsequently added and the mixture is heated to a bath temperature of 150° C. in order continuously to distill off excess triethylamine and the resulting ethanol. After 3 hours, the reaction mixture is cooled to a temperature of 40° C. and introduced into 500 ml of an ice/water mixture. The reaction mixture is rendered alkaline using 100 ml of aqueous 1N sodium hydroxide solution, and the aqueous phase (containing the product) is washed twice with ethyl acetate. After then washing the organic phase twice with aqueous 1N sodium hydroxide solution, the aqueous phases are combined, the remaining xylene is distilled off and the combined aqueous phases are adjusted to pH 2-3 using 4N HCl with cooling. The precipitated product obtained is poured onto a suction filter, and the filtration residue is washed with water and briefly with hexane, and then dried in vacuo at a temperature of 60° C. over P₂O₅. 34.6 g of (6) are obtained in the form of a slightly beige solid having a melting point of from 242 to 244° C. (decomposition).

Example P4

A catalytic amount of 4-dimethylaminopyridine is added to a solution, cooled to a temperature of 0° C., of 3 g (10.4 mmol) of (6) and 1.6 g (15.8 mmol) of triethylamine in 100 ml of tetrahydrofuran. 1.57 g (13.0 mmol) of pivaloyl chloride is then added dropwise. After stirring for 30 minutes at a temperature of 0° C., the cooling is removed and the stirring is continued for a further 60 minutes. The reaction mixture is then introduced into saturated aqueous sodium chloride solution and the organic phase is separated off. The organic phase is dried over magnesium sulfate, filtered off and concentrated by evaporation. After purification by chromatography and recrystallisation from diethyl ether, 2.94 g of (7) having a melting point of from 135 to 136° C. are obtained.

Example P5 Preparation of 2-(2,6-diethyl-4-methyl-phenyl)-tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione

1.39 g of tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione and 2.68 g of sodium tertiary butanolate are dissolved at 20° in 20 ml of dimethylformamide, and 3.21 g of 2,6-diethyl-4-methyl-iodobenzene and 0.82 g of Pd(TPP)₂Cl₂ are added. Stirring is then carried out for 2.5 hours at 125°. After cooling to room temperature, 200 ml of ethyl acetate and 200 ml of ether are added and the reaction mixture is poured onto a suction filter. 100 ml of water and 100 ml of methylene chloride are added to the filtration residue, and acidification is carried out using hydrochloric acid. The organic phase is separated off, dried and concentrated by evaporation.

The residue (1.9 g) is chromatographed on silica gel (ethyl acetate/hexane 3:1). 2-(2,6-Diethyl-4-methyl-phenyl)-tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione is obtained in the form of beige crystals having a melting point of from 174 to 175°.

Example P6 Preparation of 2-(2,6-diethyl-4-methyl-phenyl)-tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione

1.39 g of tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione and 2.68 g of sodium tertiary butanolate are dissolved at 20° in 20 ml of dimethylformamide, and 2.66 g of 2,6-diethyl-4-methyl-bromobenzene as well as 0.82 g of Pd(TPP)₂Cl₂ are added. Stirring is then carried out for 2.5 hours at 125°. After cooling to room temperature, 200 ml of ethyl acetate and 200 ml of ether are added, and the reaction mixture is poured onto a suction filter. 100 ml of water and 100 ml of methylene chloride are added to the filtration residue and acidification is carried out using hydrochloric acid. The organic phase is separated off, dried and concentrated by evaporation. The residue (1.4 g) is chromatographed on silica gel (ethyl acetate/hexane 3:1).

2-(2,6-Diethyl-4-methyl-phenyl)-tetrahydro-pyrazolo[1,2-a]pyridazine-1,3-dione is obtained in the form of beige crystals having a melting point of from 174 to 175°.

In the following Tables, the melting points are quoted in ° C. Me denotes the methyl group. Where a formula is given for the substituents G₁ to G₁₀ and R₄ and R₅ (independently of each other), the left-hand side of that formula is the linking point to the oxygen atom of the heterocycle Q₁ to Q₁₀. In the case of the substituent meaning of R₄ and R₅ together, the right-hand side of the molecule is the linking point to the heterocycle Q₁. The remaining terminal valencies are methyl groups.

In the following Tables, “LC/MS: M+” expresses in daltons the positively charged molecular ion that has been ascertained from the mass spectrum in the analysis of the product by coupled HPLC (High Performance Liquid Chromatography) and MS (Mass Spectrometry) devices.

TABLE 1 Compounds of formula Ia: (Ia)

No. R₁ R₃ R₄/R₅ G₁ Physical data 1.1 ethyl ethyl —(CH₂)₄— —H m.p. 209-211 1.2 ethyl ethyl —(CH₂)₄—

m.p. 125-127 1.3 ethyl ethyl

m.p. 195 1.4 ethyl ethyl

m.p. 180 1.5 ethyl ethyl

—H wax 1.6 ethyl ethyl

solid 1.1 ethyl ethyl

crystalline 1.2 ethyl ethyl

—H crystalline 1.3 ethyl ethyl

—H solid 1.4 ethyl ethyl

—H solid 1.5 ethyl ethyl

—H solid 1.6 ethyl ethyl

m.p. 153-155 1.7 ethyl ethyl

oil 1.8 ethyl ethyl

oil 1.9 ethyl ethyl

solid 1.10 ethyl ethyl

—H solid 1.11 ethyl ethyl

—H viscous 1.12 ethyl ethyl

—H viscous 1.13 ethyl ethyl

—H viscous 1.14 ethyl ethyl

—H viscous 1.15 ethyl ethyl

—H viscous 1.16 ethyl ethyl

viscous 1.17 ethyl ethyl

—H viscous 1.18 ethyl ethyl

—H solid 1.19 ethyl ethyl

—H solid 1.20 ethyl ethyl

solid 1.21 ethyl ethyl

oil 1.22 ethyl ethyl

viscous 1.23 ethyl ethyl

—H viscous 1.24 ethyl ethyl

—H viscous 1.25 ethyl ethyl

viscous 1.26 ethyl ethyl

—H viscous 1.27 ethyl ethyl

—H solid 1.28 ethyl ethyl

solid 1.29 ethyl ethyl

—H crystalline 1.30 ethyl ethyl

—H wax 1.31 ethyl ethyl

viscous 1.32 ethyl ethyl

viscous 1.33 ethyl ethyl

—H solid 1.34 ethyl ethyl

wax 1.35 ethyl ethyl

—H amorphous 1.36 ethyl ethyl

—H wax 1.37 ethyl ethyl

oil 1.38 ethyl ethyl

—H crystalline 1.39 ethyl ethyl

—H solid 1.40 ethyl ethyl

solid 1.41 ethyl ethyl

—H m.p. 283 1.42 ethyl ethyl

—H m.p. 227 1.43 ethyl ethyl

m.p. 122-124 1.44 ethyl ethyl

—H m.p. 148-151 1.45 ethyl ethynyl

—H m.p. 163-166 1.46 ethyl ethynyl

m.p. 114-116 1.47 ethyl ethyl

—H solid 1.48 ethyl ethyl —(CH₂)₄—

1.49 ethyl ethyl —(CH₂)₄—

1.50 ethyl ethyl —(CH₂)₄—

1.51 ethyl ethyl —(CH₂)₄—

1.52 ethyl ethyl —(CH₂)₄—

1.53 ethyl ethyl —(CH₂)₄—

1.54 ethyl ethyl —(CH₂)₄—

1.55 ethyl ethyl —(CH₂)₄—

1.56 ethyl ethyl —(CH₂)₄—

1.57 ethyl ethyl —(CH₂)₄—

1.58 ethyl ethyl —(CH₂)₄—

1.59 ethyl ethyl —(CH₂)₄— —CH₂—OMe 1.60 ethyl ethyl —(CH₂)₄— —CH₂—SMe 1.61 ethyl ethyl —(CH₂)₄—

1.62 ethyl ethyl —(CH₂)₄—

1.63 ethyl ethyl —(CH₂)₄—

1.64 ethyl ethyl —(CH₂)₄—

1.65 ethyl ethyl —(CH₂)₄—

1.66 MeO— ethyl —(CH₂)₄—

m.p. 143-144° C. 1.67 ethyl- ethynyl —(CH₂)₄—

1.68 —OCHF₂ ethyl —(CH₂)₄—

1.69 —CHO ethyl —(CH₂)₄—

1.70

ethyl —(CH₂)₄—

1.71

ethyl —(CH₂)₄—

1.72 MeO— MeO— —(CH₂)₄

1.73 MeO— ethyl —(CH₂)₄— —H m.p. 159-161° C. 1.74 ethyl- ethynyl —(CH₂)₄— —H 1.75 —OCHF₂ ethyl —(CH₂)₄— —H 1.76 —CHO ethyl —(CH₂)₄— —H 1.77

ethyl —(CH₂)₄— —H 1.78

ethyl —(CH₂)₄— —H 1.79 MeO— MeO— —(CH₂)₄— —H 1.80 MeO— ethyl —(CH₂)₄— —CO₂C₂H₅ m.p. 112-113° C. 1.81 ethyl ethyl

—H m.p. 283° C. (decomposition) 1.82 ethyl ethyl

—H m.p. 140° C. 1.83 MeO— ethyl

—H solid 1.84 MeO— ethyl

wax 1.85 MeO— ethyl

—H m.p. 177-180° C. 1.86 MeO— ethyl

—H m.p. 208-210° C. 1.87 MeO— ethyl

m.p. 102-104° C. 1.88 ethyl ethyl

—H m.p. 193-194° C. (trans) 1.89 ethyl ethyl

m.p. 163-165° C. (trans) 1.90 ethyl ethyl

solid (trans) 1.91 ethyl ethyl

—H wax 1.92 ethyl ethyl

wax 1.93 ethyl ethyl

—H wax 1.94 ethyl ethyl

wax 1.95 ethyl ethyl

viscous 1.96 ethyl ethyl

—H m.p. 200-202° C. 1.97 ethyl ethyl

—H m.p. 210-220° C. (decomposition) 1.98 ethyl ethyl

—H solid 1.99 ethyl ethynyl

—H wax 1.100 ethyl ethynyl

wax 1.101 ethyl ethyl

viscous 1.102 ethyl ethyl

—H wax 1.103 OCH₃ ethyl

wax 1.104 ethyl ethyl

wax 1.105 ethyl ethyl

wax 1.106 ethyl ethyl

wax 1.107 ethyl ethyl

wax 1.108 ethyl ethyl

wax 1.109 ethyl ethyl

wax 1.110 ethyl ethyl

wax 1.111 ethynyl ethyl

wax 1.112 ethynyl ethyl

wax 1.113 ethynyl ethyl

wax 1.114 ethynyl ethyl

wax 1.115 ethynyl ethyl

wax 1.116 ethyl ethyl

—H wax 1.117 ethyl ethyl

—H wax 1.118 ethyl ethynyl

—H wax 1.119 ethyl ethynyl

—H wax 1.120 OCH₃ ethyl

—H m.p. 130-136° C. 1.121 OCH₃ ethyl

—H m.p. 198-200° C. 1.122 ethyl ethyl

wax 1.123 ethyl OCH₃

wax 1.124 ethynyl ethyl

wax 1.125 ethynyl ethyl

wax 1.126 ethynyl ethyl

wax 1.127 ethyl ethyl

—H 1.128 ethyl ethyl

1.129 OCH₃ ethyl

wax (LC/MS: M⁺ = 552) 1.130 OCH₃ ethyl

wax (LC/MS: M⁺ = 590) 1.131 OCH₃ ethyl

wax (LC/MS: M⁺ = 535) 1.132 OCH₃ ethyl

wax (LC/MS: M⁺ = 546) 1.133 OCH₃ ethyl

wax (LC/MS: M⁺ = 584) 1.134 OCH₃ ethyl

wax (LC/MS: M⁺ = 550) 1.135 OCH₃ ethyl

wax (LC/MS: M⁺ = 482) 1.136 OCH₃ ethyl

wax (LC/MS: M⁺ = 550) 1.137 OCH₃ ethyl

wax (LC/MS: M⁺ = 568) 1.138 OCH₃ ethyl

wax (LC/MS: M⁺ = 574) 1.139 OCH₃ ethyl

wax (LC/MS: M⁺ = 580) 1.140 OCH₃ ethyl

wax (LC/MS: M⁺ = 552) 1.141 OCH₃ ethyl

wax (LC/MS: M⁺ = 550) 1.142 OCH₃ ethyl

wax (LC/MS: M⁺ = 561) 1.143 OCH₃ ethyl

wax (LC/MS: M⁺ = 520) 1.144 OCH₃ ethyl

—S(O)₂CH₃ wax (LC/MS: M⁺ = 454) 1.145 OCH₃ ethyl

wax (LC/MS: M⁺ = 516) 1.146 OCH₃ ethyl

wax (LC/MS: M⁺ = 584) 1.147 OCH₃ ethyl

wax (LC/MS: M⁺ = 468) 1.148 OCH₃ ethyl

wax (LC/MS: M⁺ = 496) 1.149 OCH₃ ethyl

wax (LC/MS: M⁺ = 552) 1.150 OCH₃ ethyl

wax (LC/MS: M⁺ = 541) 1.151 ethyl ethyl

wax (LC/MS: M⁺ = 582) 1.152 ethyl ethyl

wax (LC/MS: M⁺ = 620) 1.153 ethyl ethyl

wax (LC/MS: M⁺ = 565) 1.154 ethyl ethyl

wax (LC/MS: M⁺ = 576) 1.155 ethyl ethyl

wax (LC/MS: M⁺ = 614) 1.156 ethyl ethyl

wax (LC/MS: M⁺ = 580) 1.157 ethyl ethyl

wax (LC/MS: M⁺ = 512) 1.158 ethyl ethyl

wax (LC/MS: M⁺ = 580) 1.159 ethyl ethyl

wax (LC/MS: M⁺ = 642) 1.160 ethyl ethyl

wax (LC/MS: M⁺ = 598) 1.161 ethyl ethyl

wax (LC/MS: M⁺ = 604) 1.162 ethyl ethyl

wax (LC/MS: M⁺ = 546) 1.163 ethyl ethyl

wax (LC/MS: M⁺ = 582) 1.164 ethyl ethyl

wax (LC/MS: M⁺ = 580) 1.165 ethyl ethyl

wax (LC/MS: M⁺ = 591) 1.166 ethyl ethyl

wax (LC/MS: M⁺ = 550) 1.167 ethyl ethyl

—S(O)₂CH₃ wax (LC/MS: M⁺ = 484) 1.168 ethyl ethyl

wax (LC/MS: M⁺ = 546) 1.169 ethyl ethyl

wax (LC/MS: M⁺ = 614) 1.170 ethyl ethyl

wax (LC/MS: M⁺ = 512) 1.171 ethyl ethyl

wax (LC/MS: M⁺ = 498) 1.172 ethyl ethyl

wax (LC/MS: M⁺ = 526) 1.173 ethyl ethyl

wax (LC/MS: M⁺ = 582) 1.174 ethyl ethyl

wax (LC/MS: M⁺ = 571) 1.175 ethyl ethyl

wax (LC/MS: M⁺ = 550) 1.176 ethyl ethyl

wax (LC/MS: M⁺ = 588) 1.177 ethyl ethyl

wax (LC/MS: M⁺ = 533) 1.178 ethyl ethyl

wax (LC/MS: M⁺ = 544) 1.179 ethyl ethyl

wax (LC/MS: M⁺ = 582) 1.180 ethyl ethyl

wax (LC/MS: M⁺ = 548) 1.181 ethyl ethyl

wax (LC/MS: M⁺ = 480) 1.182 ethyl ethyl

wax (LC/MS: M⁺ = 548) 1.183 ethyl ethyl

wax (LC/MS: M⁺ = 566) 1.184 ethyl ethyl

wax (LC/MS: M⁺ = 572) 1.185 ethyl ethyl

wax (LC/MS: M⁺ = 514) 1.186 ethyl ethyl

wax (LC/MS: M⁺ = 550) 1.187 ethyl ethyl

wax (LC/MS: M⁺ = 548) 1.188 ethyl ethyl

wax (LC/MS: M⁺ = 559) 1.189 ethyl ethyl

wax (LC/MS: M⁺ = 518) 1.190 ethyl ethyl

—S(O)₂CH₃ wax (LC/MS: M⁺ = 452) 1.191 ethyl ethyl

wax (LC/MS: M⁺ = 514) 1.192 ethyl ethyl

wax (LC/MS: M⁺ = 582) 1.193 ethyl ethyl

wax (LC/MS: M⁺ = 480) 1.194 ethyl ethyl

wax (LC/MS: M⁺ = 466) 1.195 ethyl ethyl

wax (LC/MS: M⁺ = 494) 1.196 ethyl ethyl

wax (LC/MS: M⁺ = 550) 1.197 ethyl ethyl

wax (LC/MS: M⁺ = 539) 1.198 ethyl ethyl

wax (LC/MS: M⁺ = 572) 1.199 OCH₃ OCH₃ —(CH₂)₄— —H m.p. 180-193° C. 1.200 ethyl ethyl

—CO₂C₂H₅ m.p. 153-154° C.

TABLE 2 Compounds of formula Ia: (Ia)

No. R₁ R₃ R₄ R₅ G₁ Physical data 2.01 ethyl ethyl methyl

—H wax 2.02 ethyl ethyl methyl

—H solid 2.03 ethyl ethyl methyl

—H solid 2.04 ethyl ethyl methyl

wax 2.05 ethyl ethyl methyl

wax 2.06 ethyl ethyl

—H m.p. 171-172 2.07 ethyl ethyl

wax 2.08 ethyl ethyl

—H amorphous 2.09 ethyl ethyl

amorphous 2.10 ethyl ethyl

—H 2.11 ethyl ethyl methyl methyl

2.12 ethyl ethyl methyl methyl —SO₂CH₃ 2.13 ethyl MeO— methyl methyl

2.14 ethyl ethynyl methyl methyl

2.15 ethyl ethyl methyl -phenyl

2.16 ethyl ethyl methyl -3-pyridyl

2.17 ethyl ethyl methyl -2-thienyl

2.18 ethyl ethyl methyl -allyl

2.19 ethyl ethyl methyl -crotyl

2.20 ethyl ethyl methyl -4-chloro-phenyl

2.21 MeO— MeO— methyl allyl —H 2.22 ethynyl ethyl phenyl- phenyl —H 2.23 ethynyl ethyl phenyl

—H 2.24 ethyl ethyl

methyl- —H 2.25 ethyl ethyl

methyl- —H 2.26 ethyl ethyl phenyl

—H 2.27 ethyl ethyl

methyl- —H 2.28 ethyl ethyl -benzyl methyl- —H 2.29 ethyl ethyl

methyl- —H 2.30 ethyl ethyl

methyl- —H 2.31 ethyl ethyl

methyl- —H 2.32 ethyl ethyl —(CH₂)₂OH allyl —H m.p. 180-185° C. (decomp.)

TABLE 3 Compounds of formula Ib: (Ib)

No. R₁ R₃ R₆ R₇ R₈ G₂ Physical data 3.01 ethyl ethyl —Me —Me —Me —H m.p. 249-254° C. 3.02 ethyl ethyl —Me —H —Me —H 3.03 ethyl ethyl —CH₂—CH₂—O—CH₂—CH₂— —Me —H 3.04 ethynyl ethyl —CH₂—CH₂— -allyl —H 3.05 ethyl ethyl —CH₂—C(Cl)₂— —Me

3.06 ethyl ethyl —(CH₂)₂— —Me —H 3.07 ethyl ethyl —(CH₂)₂—CH(CH₃)—(CH₂)₂— —Me —H 3.08 ethyl ethyl —(CH₂)₂—C(CH₃)₂—(CH₂)₂— —Me —H 3.09 ethynyl ethyl —(CH₂)₄— —Me —H 3.10 MeO— ethyl —(CH₂)₂— —H —H 3.11 MeO— ethyl —(CH₂)₂— -methyl

3.12 —C(O)CH₃ ethyl —(CH₂)₂— methyl —H 3.13 —OCHF₂ ethyl —(CH₂)₂— methyl

3.14 ethyl ethyl —(CH₂)₃— methyl

3.15 ethyl ethyl —(CH₂)₅— —H —H m.p. 222-224° C. 3.16 ethyl ethyl —(CH₂)₅— —H

m.p. 147-149° C. 3.17 ethyl ethyl methyl methyl —H —H m.p. 244-246° C. 3.18 ethyl ethyl methyl methyl —H

m.p. 164-166° C. 3.19 ethyl ethyl —(CH₂)₅— -n-C₄H₉ —H m.p. 170-175° C. 3.20 ethyl ethyl —(CH₂)₅— -n-C₄H₉

m.p. 99-101° C. 3.21 ethyl ethyl —(CH₂)₅— C₃H₆OMe —H solid 3.22 ethyl ethyl methyl methyl methyl

m.p. 94-101° C. 3.23 ethyl ethyl —(CH₂)₅— methyl —H m.p. 252-262° C. 3.24 ethyl ethyl —(CH₂)₅— methyl

m.p. 127-128° C. 3.25 ethyl ethyl

—H crystalline 3.26 ethyl ethyl

wax 3.27 ethyl ethyl

—H crystalline 3.28 ethyl ethyl

crystalline 3.29 ethyl ethyl

—H solid 3.30 ethyl ethyl

—H solid 3.31 ethyl ethyl

3.32 ethyl ethyl

—H amorphous No. R₁ R₃ R₇ R₆ R₈ G₂ Physical data 3.33 ethyl ethyl methyl —(CH₂)₄—

3.34 ethyl ethyl methyl —(CH₂)₃—

3.35 ethyl ethyl —H

—H 3.36 ethyl ethyl —H

3.37 ethyl ethyl —H

3.38 ethyl ethyl —H

—H 3.39 ethyl ethyl —H

3.40 ethyl ethyl —H

—H 3.41 ethyl ethyl —H

3.42 ethyl ethyl —H

—H 3.43 ethyl ethyl —H

3.44 ethyl ethyl —H

—H 3.45 ethyl ethyl —H

TABLE 4 Compounds of formula Ic: (Ic)

No. R₁ R₃ R₂ R₃₁ G₃ Physical Data 4.01 ethyl ethyl methyl methyl —H m.p. 224-226° C. 4.02 ethyl ethyl methyl methyl

m.p. 102-104° C. 4.03 ethyl ethyl methyl ethyl —H 4.04 ethyl ethynyl methyl methyl —H 4.05 ethyl ethynyl methyl methyl

4.06 ethyl methoxy methyl methyl —H 4.07 ethyl ethyl —(CH₂)₂— —H 4.08 ethyl ethyl —(CH₂)₂—CH(CH₃)—(CH₂)₂—

4.09 ethyl ethyl —(CH₂)₂—C(CH₃)₂—(CH₂)₂—

4.10 ethyl ethyl —(CH₂)₄— —H 4.11 ethyl ethyl —CH₂—CH₂—O—CH₂—CH₂—

4.12 ethyl ethyl methyl isopropyl —H 4.13 ethyl ethyl methyl ethyl —H 4.14 ethyl ethyl methyl n-butyl

4.15 ethyl ethyl methyl H

4.16 ethyl ethyl —H —H —H m.p. 176-178° C. 4.17 ethyl ethyl —H —H

m.p. 80-82° C. 4.18 OCH₃ ethyl —H —H —H m.p. 169-171° C. 4.19 OCH₃ ethyl —H —H

oil

TABLE 5 Compounds of formula Id: (Id)

No. R₁ R₃ R₃₂ R₃₃ G₄ Physical data 5.01 ethyl ethyl methyl methyl —H m.p. 181-183° C. 5.02 ethyl ethyl methyl methyl

oil 5.03 ethyl ethyl methyl ethyl —H 5.04 ethyl ethynyl methyl methyl —H 5.05 ethyl ethynyl methyl methyl

5.06 ethyl methoxy methyl methyl —H 5.07 ethyl ethyl —(CH₂)₂— —H 5.08 ethyl ethyl —(CH₂)₂—CH(CH₃)—(CH₂)₂—

5.09 ethyl ethyl —(CH₂)₂—C(CH₃)₂—(CH₂)₂—

5.10 ethyl ethyl —(CH₂)₄—

5.11 ethyl ethyl —CH₂—CH₂—O—CH₂—CH₂—

5.12 ethyl ethyl methyl isopropyl —H 5.13 ethyl ethyl methyl ethyl —H 5.14 ethyl ethyl methyl n-butyl

5.15 ethyl ethyl methyl H

5.16 ethyl ethyl methyl H —H oil

TABLE 6 Compounds of formula Ie: (Ie)

No. R₁ R₃ R₉ R₁₀ R₁₁ R₁₂ G₅ Physical data 6.01 ethyl ethyl methyl —H methyl —H

6.02 ethyl ethyl methyl methyl —H —H

6.03 ethyl ethyl —(CH₂)₂— —H —H —H 6.04 ethyl ethyl —(CH₂)₄— methyl —H —H 6.05 ethyl ethyl —(CH₂)₂—O—(CH₂)₂— —H —H

6.06 ethyl ethyl —H methyl —(CH₂)₄—

6.07 ethyl ethyl —H —O— —H

6.08 ethyl ethyl —H —CH₂— —H

6.09 ethyl ethynyl —H —(CH₂)₃— —H

6.10 ethyl MeO— —H —(CH₂)₄— —H

6.11 ethyl ethynyl —H —(CH₂)₄— —H

TABLE 7 Compounds of formula If: (If)

No. R₁ R₂ R₁₃ R₁₄ G₆ Phys. data 7.01 ethyl ethyl methyl methyl —H 7.02 ethyl ethyl methyl —H —H 7.03 ethyl ethyl —H methyl —H 7.04 ethyl ethyl ethyl methyl —H 7.05 ethyl ethyl —(CH₂)₄— —H 7.06 ethyl MeO— —(CH₂)₄— —H 7.07 ethyl ethynyl —(CH₂)₄—

7.08 ethyl ethynyl —(CH₂)₃— —H

TABLE 8 Compounds of formula Ig: (Ig)

No. R₁ R₂ R₃₄ R₃₅ G₇ Phys. data 8.01 ethyl ethyl methyl methyl —H 8.02 ethyl ethyl methyl —H —H 8.03 ethyl ethyl —H methyl —H 8.04 ethyl ethyl ethyl methyl —H 8.05 ethyl ethyl —(CH₂)₄—

8.06 ethyl ethyl —(CH₂)₃—

8.07 ethyl ethynyl methyl methyl

8.08 ethyl methoxy methyl methyl

TABLE 9 Compounds of formula Ih: (Ih)

No. R₁ R₃ R₁₅ G₈ Physical data 9.01 ethyl ethyl methyl —H 9.02 ethyl methoxy phenyl —H 9.03 ethyl ethynyl -4-chloro- —H phenyl 9.04 ethyl ethyl ethyl

9.05 ethyl ethyl —OMe

9.06 ethyl ethyl —CF₃

9.07 ethyl ethyl isopropyl

9.08 ethyl ethyl n-butyl

9.09 ethyl ethyl cyclopropyl

9.10 ethyl ethyl phenyl —H m.p. 208-209° C. 9.11 ethyl ethyl phenyl

m.p. 147-149° C. 9.12 ethyl ethyl -4-tert-butyl- —H m.p. phenyl 222-224° C. 9.13 ethyl ethyl -4-tert-butyl phenyl

amorphous 9.14 ethyl ethyl -4-tolyl —H 9.15 ethyl ethyl -4-tolyl

9.16 ethyl ethyl -3-chloro-4- —H m.p. fluorophenyl 186-188° C. 9.17 ethyl ethyl -3-chloro-4- fluorophenyl

m.p. 109-110° C.

TABLE 10 Compounds of formula Ik: (Ik)

No. R₁ R₃ R₁₆ Y R₁₇ R₁₈ G₉ Phys. data 10.01 ethyl ethyl methyl O methyl —H

10.02 ethyl ethyl methyl O methyl methyl

10.03 ethyl ethyl methyl N—CH₃ methyl methyl

10.04 ethyl ethyl methyl

—H

10.05 ethyl ethyl methyl —CH₂— methyl methyl

10.06 ethyl ethyl methyl —CH₂— methyl —H

10.07 ethyl ethyl ethyl —CH₂— —(CH₂)₂—

10.08 ethyl ethynyl methyl —CH₂— —H methyl

10.09 ethyl MeO— methyl —CH₂— methyl methyl

10.10 ethyl ethyl methyl O methyl —H —H 10.11 ethyl ethyl methyl O methyl methyl —H 10.12 ethyl ethyl methyl N—CH₃ methyl methyl —H 10.13 ethyl ethyl methyl

—H —H 10.14 ethyl ethyl methyl —CH₂— methyl methyl —H 10.15 ethyl ethyl methyl —CH₂— methyl —H —H 10.16 ethyl ethyl ethyl —CH₂— —(CH₂)₂— —H 10.17 ethyl ethynyl methyl —CH₂— —H methyl —H 10.18 ethyl MeO— methyl —CH₂— methyl methyl —H In the following Table 21, Me is methyl, Et is ethyl, Pr is propyl and Bu is butyl;

TABLE 21 Compounds of formula Im: (Im)

Comp. No. R₁ R₃ R₅₅ R₁₃₇ R₁₃₈ R₁₃₉ G₁₀ Y₂ Phys. data 21.1 Et Et H H H H H O 21.2 Et ethynyl H H H H H O 21.3 Et Et Me Me Me Me H O 21.4 Et OMe Me Me Me Me H O 21.5 Et Et Me H H H H O 21.6 ethynyl Et Me H H H H O 21.7 Et Et H H Me Me H O 21.8 OMe Et H H Me Me H O 21.9 Et Et Me H Me Me H O 21.10 Et ethynyl Me H Me Me H O 21.11 Et Et H Me H Me H O 21.12 Et OMe H Me H Me H O 21.13 Et Et Me Et H H H O 21.14 ethynyl Et Me Et H H H O 21.15 Et Et H Et H Et H O 21.16 OMe Et H Et H Et H O 21.17 Et Et H H —(CH₂)₄— H O 21.18 Et ethynyl H H —(CH₂)₄— H O 21.19 Et Et H H H H COCMe₃ O 21.20 Et ethynyl H H H H SO₂Me O 21.21 Et Et Me Me Me Me COCMe₃ O 21.22 Et OMe Me Me Me Me SO₂-n-Pr O 21.23 Et Et Me H H H COCMe₃ O 21.24 ethynyl Et Me H H H SO₂-n-Bu O 21.25 Et Et H H Me Me COCMe₃ O 21.26 OMe Et H H Me Me SO₂C₈H₁₇ O 21.27 Et Et Me H Me Me COCMe₃ O 21.28 Et ethynyl Me H Me Me SO₂Ph O 21.29 Et Et H Me H Me COCMe₃ O 21.30 Et OMe H Me H Me SO₂Me O 21.31 Et Et Me Et H H COCMe₃ O 21.32 ethynyl Et Me Et H H COCMe₃ O 21.33 Et Et H Et H Et COCMe₃ O 21.34 OMe Et H Et H Et COCMe₃ O 21.35 Et Et H H —(CH₂)₄— COCMe₃ O 21.36 Et ethynyl H H —(CH₂)₄— COCMe₃ O 21.37 Et Et H H H H H S 21.38 Et ethynyl H H H H H S 21.39 Et Et Me Me Me Me H S 21.40 Et OMe Me Me Me Me H S 21.41 Et Et Me H H H H S 21.42 ethynyl Et Me H H H H S 21.43 Et Et H H Me Me H S 21.44 OMe Et H H Me Me H S 21.45 Et Et Me H Me Me H S 21.46 Et ethynyl Me H Me Me H S 21.47 Et Et H Me H Me H S 21.48 Et OMe H Me H Me H S 21.49 Et Et Me Et H H H S 21.50 ethynyl Et Me Et H H H S 21.51 Et Et H Et H Et H S 21.52 OMe Et H Et H Et H S 21.53 Et Et H H —(CH₂)₄— H S 21.54 Et ethynyl H H —(CH₂)₄— H S 21.55 Et Et H H H H COCMe₃ S 21.56 Et ethynyl H H H H SO₂Me S 21.57 Et Et Me Me Me Me COCMe₃ S 21.58 Et OMe Me Me Me Me SO₂-n-Pr S 21.59 Et Et Me H H H COCMe₃ S 21.60 ethynyl Et Me H H H SO₂-n-Bu S 21.61 Et Et H H Me Me COCMe₃ S 21.62 OMe Et H H Me Me SO₂C₈H₁₇ S 21.63 Et Et Me H Me Me COCMe₃ S 21.64 Et ethynyl Me H Me Me SO₂Ph S 21.65 Et Et H Me H Me COCMe₃ S 21.66 Et OMe H Me H Me SO₂Me S 21.67 Et Et Me Et H H COCMe₃ S 21.68 ethynyl Et Me Et H H COCMe₃ S 21.69 Et Et H Et H Et COCMe₃ S 21.70 OMe Et H Et H Et COCMe₃ S 21.71 Et Et H H —(CH₂)₄— COCMe₃ S 21.72 Et ethynyl H H —(CH₂)₄— COCMe₃ S 21.73 Et Et H H H H H NCH(CH₃)₂ 21.74 Et Et H H H H H NCH₃ 21.75 Et Et H H H H H NCH₂Ph 21.76 Et ethynyl H H H H H NCH₃ 21.77 Et Et Me Me Me Me H NCH(CH₃)₂ 21.78 Et OMe Me Me Me Me H NCH₃ 21.79 Et Et Me H H H H NCH(CH₃)₂ 21.80 ethynyl Et Me H H H H NCH₃ 21.81 Et Et H H Me Me H NCH₃ 21.82 OMe Et H H Me Me H NCH(CH₃)₂ 21.83 Et Et Me H Me Me H NCH₂Ph 21.84 Et ethynyl Me H Me Me H NCH₃ 21.85 Et Et H Me H Me H NCH₂Ph 21.86 Et OMe H Me H Me H NCH₃ 21.87 Et Et Me Et H H H NCH(CH₃)₂ 21.88 ethynyl Et Me Et H H H NCH₃ 21.89 Et Et H Et H Et H NCH₂Ph 21.90 OMe Et H Et H Et H NCH(CH₃)₂ 21.91 Et Et H H —(CH₂)₄— H NCH(CH₃)₂ 21.92 Et ethynyl H H —(CH₂)₄— H NCH₃ 21.93 OMe Et Et Me H H H NCH₃ 21.94 Et Et H H H H COCMe₃ NCH(CH₃)₂ 21.95 Et Et H H H H SO₂Me NCH₃ 21.96 Et Et H H H H COCMe₃ NCH₂Ph 21.97 Et ethynyl H H H H SO₂-n-Pr NCH₃ 21.98 Et Et Me Me Me Me COCMe₃ NCH(CH₃)₂ 21.99 Et OMe Me Me Me Me SO₂-n-Bu NCH₃ 21.100 Et Et Me H H H COCMe₃ NCH(CH₃)₂ 21.101 ethynyl Et Me H H H SO₂C₈H₁₇ NCH₃ 21.102 Et Et H H Me Me COCMe₃ NCH₃ 21.103 OMe Et H H Me Me SO₂Ph NCH(CH₃)₂ 21.104 Et Et Me H Me Me COCMe₃ NCH₂Ph 21.105 Et ethynyl Me H Me Me SO₂Me NCH₃ 21.106 Et Et H Me H Me COCMe₃ NCH₂Ph 21.107 Et OMe H Me H Me COCMe₃ NCH₃ 21.108 Et Et Me Et H H COCMe₃ NCH(CH₃)₂ 21.109 ethynyl Et Me Et H H COCMe₃ NCH₃ 21.110 Et Et H Et H Et COCMe₃ NCH₂Ph 21.111 OMe Et H Et H Et COCMe₃ NCH(CH₃)₂ 21.112 Et Et H H —(CH₂)₄— COCMe₃ NCH(CH₃)₂ 21.113 Et ethynyl H H —(CH₂)₄— SO₂C₈H₁₇ NCH₃ 21.114 OMe Et Et Me H H SO₂-n-Bu NCH₃ 21.115 Et Et H —(CH₂)₂— H H CH₂ 21.116 Et ethynyl H —(CH₂)₂— H H CH₂ 21.117 Et Et —(CH₂)₂— H H H CH₂ 21.118 Et OMe —(CH₂)₂— H H H CH₂ 21.119 Et Et H Me Me H H CH₂ 21.120 ethynyl Et H Me Me H H CH₂ 21.121 Et Et Et H H H H CH₂ 21.122 OMe Et Et H H H H CH₂ 21.123 Et Et H H Me Me H CH₂ 21.124 Et ethynyl H H Me Me H CH₂ 21.125 Et Et H OMe H H H CH₂ 21.126 Et OMe H OMe H H H CH₂ 21.127 Et Et H —(CH₂)₃— H H CH₂ 21.128 ethynyl Et H —(CH₂)₃— H H CH₂ 21.129 Et Et Me H Me Me H CH₂ 21.130 OMe Et Me H Me Me H CH₂ 21.131 Et Et Me OMe H H H CH₂ 21.132 Et ethynyl Me OMe H H H CH₂ 21.133 Et Et H SMe H H H CH₂ 21.134 Et OMe H SMe H H H CH₂ 21.135 Et Et Me Me Me Me H CH₂ 21.136 ethynyl Et Me Me Me Me H CH₂ 21.137 Et Et OH Me Me Me H CH₂ 21.138 OMe Et OH Me Me Me H CH₂ 21.139 Et Et Me SMe H H H CH₂ 21.140 Et ethynyl Me SMe H H H CH₂ 21.141 Et Et Et Et H Me H CH₂ 21.142 Et ethynyl Et Et H Me H CH₂ 21.143 Et Et Me Me H CH₂OMe H CH₂ 21.144 Et OMe Me Me H CH₂OMe H CH₂ 21.145 Et ethynyl Me SMe H OMe H CH₂ 21.146 Et Et Me SMe H OMe H CH₂ 21.147 Et OMe Me SMe H OMe H CH₂ 21.148 Et Et H —(CH₂)₂— H COCMe₃ CH₂ 21.149 Et ethynyl H —(CH₂)₂— H COCMe₃ CH₂ 21.150 Et Et —(CH₂)₂— H H SO₂-n-Pr CH₂ 21.151 Et OMe —(CH₂)₂— H H COCMe₃ CH₂ 21.152 Et Et H Me Me H COCMe₃ CH₂ 21.153 ethynyl Et H Me Me H SO₂Me CH₂ 21.154 Et Et Et H H H COCMe₃ CH₂ 21.155 OMe Et Et H H H SO₂-n-Pr CH₂ 21.156 Et Et H H Me Me COCMe₃ CH₂ 21.157 Et ethynyl H H Me Me SO₂-n-Bu CH₂ 21.158 Et Et H OMe H H COCMe₃ CH₂ 21.159 Et OMe H OMe H H SO₂C₈H₁₇ CH₂ 21.160 Et Et H —(CH₂)₃— H COCMe₃ CH₂ 21.161 ethynyl Et H —(CH₂)₃— H COCMe₃ CH₂ 21.162 Et Et Me H Me Me SO₂-n-Pr CH₂ 21.163 OMe Et Me H Me Me COCMe₃ CH₂ 21.164 Et Et Me OMe H H COCMe₃ CH₂ 21.165 Et ethynyl Me OMe H H SO₂Me CH₂ 21.166 Et Et H SMe H H COCMe₃ CH₂ 21.167 Et OMe H SMe H H SO₂-n-Pr CH₂ 21.168 Et Et Me Me Me Me COCMe₃ CH₂ 21.169 ethynyl Et Me Me Me Me SO₂-n-Bu CH₂ 21.170 Et Et OH Me Me Me COCMe₃ CH₂ 21.171 OMe Et OH Me Me Me SO₂C₈H₁₇ CH₂ 21.172 Et Et Me SMe H H COCMe₃ CH₂ 21.173 Et ethynyl Me SMe H H COCMe₃ CH₂ 21.174 Et Et Et Et H Me COCMe₃ CH₂ 21.175 Et ethynyl Et Et H Me SO₂C₈H₁₇ CH₂ 21.176 Et Et Me Me H CH₂OMe SO₂-n-Pr CH₂ 21.177 Et OMe Me Me H CH₂OMe COCMe₃ CH₂ 21.178 Et ethynyl Me SMe H OMe COCMe₃ CH₂ 21.179 Et Et Me SMe H OMe SO₂C₈H₁₇ CH₂ 21.180 Et OMe Me SMe H OMe COCMe₃ CH₂ 21.181 Et Et H —(CH₂)₂— H H CHCH₃ 21.182 Et ethynyl H —(CH₂)₂— H H CHCH₃ 21.183 Et Et —(CH₂)₂— H H H CHCH₃ 21.184 Et OMe —(CH₂)₂— H H H CHCH₃ 21.185 Et Et H Me Me H H CHCH₃ 21.186 ethynyl Et H Me Me H H CHCH₃ 21.187 Et Et Et H H H H CHCH₃ 21.188 OMe Et Et H H H H CHCH₃ 21.189 Et Et H H Me Me H CHCH₃ 21.190 Et ethynyl H H Me Me H CHCH₃ 21.191 Et Et H —(CH₂)₂— H COCMe₃ CHCH₃ 21.192 Et ethynyl H —(CH₂)₂— H COCMe₃ CHCH₃ 21.193 Et Et —(CH₂)₂— H H SO₂-n-Pr CHCH₃ 21.194 Et OMe —(CH₂)₂— H H COCMe₃ CHCH₃ 21.195 Et Et H Me Me H COCMe₃ CHCH₃ 21.196 ethynyl Et H Me Me H SO₂Me CHCH₃ 21.197 Et Et Et H H H COCMe₃ CHCH₃ 21.198 OMe Et Et H H H SO₂-n-Pr CHCH₃ 21.199 Et Et H H Me Me COCMe₃ CHCH₃ 21.200 Et ethynyl H H Me Me SO₂-n-Bu CHCH₃ 21.201 Et Et H —(CH₂)₂— H H C(CH₃)₂ 21.202 Et ethynyl H —(CH₂)₂— H H C(CH₃)₂ 21.203 Et Et —(CH₂)₂— H H H C(CH₃)₂ 21.204 Et OMe —(CH₂)₂— H H H C(CH₃)₂ 21.205 Et Et H Me Me H H C(CH₃)₂ 21.206 ethynyl Et H Me Me H H C(CH₃)₂ 21.207 Et Et Et H H H H C(CH₃)₂ 21.208 OMe Et Et H H H H C(CH₃)₂ 21.209 Et Et H —(CH₂)₂— H COCMe₃ C(CH₃)₂ 21.210 Et ethynyl H —(CH₂)₂— H COCMe₃ C(CH₃)₂ 21.211 Et Et —(CH₂)₂— H H SO₂-n-Pr C(CH₃)₂ 21.212 Et OMe —(CH₂)₂— H H COCMe₃ C(CH₃)₂ 21.213 Et Et H Me Me H COCMe₃ C(CH₃)₂ 21.214 ethynyl Et H Me Me H SO₂Me C(CH₃)₂ 21.215 Et Et Et H H H COCMe₃ C(CH₃)₂ 21.216 OMe Et Et H H H SO₂-n-Pr C(CH₃)₂ 21.217 Et Et Me Me Me Me H CHCO₂Me 21.218 Et Et H H H H H CHCO₂Me 21.219 Et Et Me Me Me Me COCMe₃ CHCO₂Me 21.220 Et Et H H H H COCMe₃ CHCO₂Me 21.221 Et OMe —(CH₂)₂— H H H CHCO₂Me 21.222 Et OMe —(CH₂)₂— H H COCMe₃ CHCO₂Me

BIOLOGICAL EXAMPLES

Comparison Test:

The following compounds were tested for their herbidical action: compound no. 1.02

according to the present invention, and compound A

Example B1 Herbicidal Action Prior to Emergence of the Plants (Pre-Emergence Action)

Monocotyledonous and dicotyledonous weeds are sown in plastics pots in standard soil. Immediately after sowing, the test substances are applied in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)) (500 liters of water/ha). The rate of application is 500 g of active substance/ha. The test plants are then grown in the greenhouse under optimum conditions. The evaluation is carried out 3 weeks after application, using a scale of nine ratings (1=total damage, 9=no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

Test plants: Alopecurus (Alo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra).

TABLE B1 Pre-emergence action: Pre-emergence action at 500 g of active ingredient/ha Comp. No. Alo Ave Lol Set Pan Sor Dig Ech Bra compound A 2 4 1 2 1 4 4 5 3 1.02 1 1 1 1 1 1 4 1 1

Example B2 Herbicidal Action after Emergence of the Plants (Post-Emergence Action)

Monocotyledonous and dicotyledonous weeds are grown in standard soil in plastics pots under greenhouse conditions. The test substances are applied to the test plants at the 3- to 6-leaf stage. The test substances are applied at a rate of application of 500 g of active substance per hectare in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)) (500 liters of water/ha). The evaluation is carried out 3 weeks after application, using a scale of nine ratings (1=total damage, 9=no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

Test plants: Alopecurus (Alo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra).

TABLE B2 Post-emergence action: Post-emergence action at 250 g of active ingredient/ha Comp. No. Alo Ave Lol Set Pan Sor Dig Ech Bra compound A 3 3 2 2 1 3 2 1 2 1.02 1 1 1 1 1 1 2 1 1

By comparing the herbicidal activity of compound A with compound no. 1.02 of the present invention, it can be seen that, in the case of all weeds tested, compound no. 1.02 surprisingly exhibits an appreciably improved herbicidal action, although the only difference between that compound and compound A is that two ethyl groups have been replaced by methyl groups.

Example B3 Herbicidal Action Prior to the Emergence of the Plants (Pre-Emergence Action) of Compounds of the Present Invention

Monocotyledonous and dicotyledonous weeds are sown in standard soil in plastics pots. Immediately after sowing, the test substances are applied in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)) (500 liters of water/ha). The rate of application is 500 g of active substance/ha. The test plants are then grown in the greenhouse under optimum conditions, The evaluation is carried out 3 weeks after application, using a scale of nine ratings (1=total damage, 9=no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

Test plants: Avena (Ave), Lolium (Lol), Setaria (Set).

TABLE B3 Pre-emergence action: MERGE ® is used as oil additive in a concentration of 0.7% by weight of the spray mixture Test plant: Comp. No. Ave Lol Set 1.01 1 1 1 1.02 1 1 1 1.31 1 1 2 1.35 1 1 1

The same results are obtained when the compounds of formula I are formulated in accordance with Examples F2 and F4 to F8.

Example B4 Herbicidal Action after the Emergence of the Plants (Post-Emergence Action) of Compounds of the Present Invention (For Description See Example B2)

Test plants: Avena (Ave), Lolium (Lol), Setaria (Set). The results are given in the following Table B4:

TABLE B4 Post-emergence action: MERGE ® is used as oil additive in a concentration of 0.7% by weight of the spray mixture. Test plant: Comp. No. Ave Lol Set 1.01 1 1 1 1.02 1 1 1 1.04 1 1 1 1.05 1 3 1 1.07 1 1 1 1.08 1 1 1 1.10 1 1 1 1.11 1 1 1 1.14 1 2 2 1.15 1 2 1 1.17 1 1 2 1.19 1 1 1 1.21 1 1 1 1.23 1 1 1 1.26 1 2 1 1.27 1 1 2 1.30 1 1 1 1.31 1 1 1 1.35 1 1 1 1.37 1 1 1 1.39 1 1 1 1.40 1 1 2 1.43 1 2 2

The same results are obtained when the compounds of formula I are formulated in accordance with Examples F2 and F4 to F8. 

1. A compound of formula I

wherein R₁ and R₃ are each independently of the other ethyl, haloethyl, ethynyl, C₁-C₂alkoxy, C₁-C₂haloalkoxy, C₁-C₂alkylcarbonyl, C₁-C₂hydroxyalkyl or C₁-C₂alkoxycarbonyl; Q is a group

R₄ and R₅ are each independently of the other C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁₀-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl, C₂-C₁₀—N-alkoxyiminoalkyl, C₂-C₁₀alkoxycarbonylalkyl, C₁-C₁₀aminoalkyl, C₃-C₁₀dialkylaminoalkyl), C₂-C₁₀alkyl-aminoalkyl, C₁-C₁₀cyanoalkyl, C₄-C₁₀cycloalkylalkyl, C₁-C₁₀phenylalkyl, C₁-C₁₀heteroarylalkyl, C₁-C₁₀phenoxyalkyl, C₁-C₁₀heteroaryloxyalkyl, C₁-C₁₀alkylideneaminooxyalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀trialkylsilylalkyl, C₂-C₁₀alkylaminocarbonylalkyl, C₂-C₁₀dialkylaminocarbonylalkyl, C₂-C₁₀alkyl-aminocarbonyloxyalkyl, C₃-C₁₀dialkylaminocarbonyloxalkyl, C₂-C₁₀alkoxy-carbonylaminoalkyl, C₁-C₁₀—N-alkoxycarbonyl-N-alkylaminoalkyl, C₁-C₁₀cycloalkyl, aryl or heteroaryl; or R₄ and R₅, together with the atoms to which they are bonded, form a 5- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur and that, in addition, may contain a fused or spiro-bound alkylene or alkenylene chain consisting of from 2 to 6 carbon atoms, which chain may in turn contain one or two hetero atoms selected from oxygen and sulfur, wherein the cyclic group may be substituted by phenyl or benzyl, which in turn may be substituted by halogen, C₁-C₆alkyl, C₁-C₆halo-alkyl, C₃-C₆cycloalkyl, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro; R₆ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkyl-sulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; R₇, is hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl or C₂-C₁₀alkoxyalkyl; R₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyl-oxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; or R₆ and R₇, together with the atom to which they are bonded, form a saturated 3- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur; or R₆ and R₈, together with the atoms to which they are bonded, form a 5- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur; R₉, R₁₀, R₁₁, and R₁₂ are each independently of the others C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkylsulfinylalkyl, C₂-C₁₀alkyl-sulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; or R₉ and R₁₁ or R₉ and R₁₀, together with the atoms to which they are bonded, form a 5- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur; R₁₆ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthiolkyl, C₂-C₁₀alkyl-sulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; R₁₇ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₂-C₁₀alkoxyalkyl, C₃-C₁₀alkenyloxyalkyl, C₃-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₂-C₁₀alkyl-sulfinylalkyl, C₂-C₁₀alkylsulfonylalkyl, C₂-C₁₀alkylcarbonylalkyl, C₃-C₁₀cycloalkyl, aryl or heteroaryl; R₁₈ is hydrogen, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀alkyl or C₁-C₁₀alkoxyalkyl; or R₁₇ and R₁₈, together with the atoms to which they are bonded, form a 3- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur; Y is oxygen, sulfur, C—R₁₉ or N—R₃₆; R₁₉ and R₃₆ are each independently of the other C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, phenyl or heteroaryl; or R₁₈ and R₁₉ or R₁₈ and R₃₆, together with the atom to which they are bonded, form a saturated 5- to 7-membered cyclic group that may contain one or two hetero atoms selected from nitrogen, oxygen and sulfur; G₁, G₂, G₅, and G₉ are each independently of the others hydrogen, —C(X₁)—R₂₀, —C(X₂)—X₃—R₂₁, —C(X₄)—N(R₂₂)—R₂₃, —SO₂—R₂₄, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation, —P(X₅)(R₂₅)—R₂₆ or —CH₂—X₆—R₂₇; X₁, X₂, X₃, X₄, X₅ and X₆ are each independently of the others oxygen or sulfur; R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the others hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylamino-C₁-C₅alkyl, C₂-C₈dialkylamino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅alkyl-sulfonyl-C₁-C₅alkyl, C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkyl-carbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅aminocarbonyl-C₁-C₅alkyl, C₂-C₈dialkylamino-carbonyl-C₁-C₅alkyl, C₁-C₅alkylcarbonylamino-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-(C₂-C₅alkyl)-aminoalkyl, C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl, C₂-C₅alkenyl, C₂C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or heteroarylamino, or heteroaryl or heteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diheteroarylamino, or diheteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, phenylamino, or phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diphenylamino, or diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy; R₂₄, R₂₅ and R₂₆ are hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylamino-C₁-C₅alkyl, C₂-C₈dialkylamino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅alkylsulfonyl-C₁-C₅alkyl, C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅aminocarbonyl-C₁-C₅alkyl, C₂-C₈alkyl-aminocarbonyl-C₁-C₅alkyl, C₁-C₅alkylcarbonylamino-C₁-C₅alkyl, C₁-C₅alky-lcarbonyl-(C₂-C₅alkyl)-aminoalkyl, C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl, C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl, or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or heteroarylamino, or heteroaryl or heteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diheteroarylamino, or diheteroarylamino substituted by C₁-C₃alkyl, C₁-C₃halo-alkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, phenylamino, or phenylamino substituted by C₁-C₃alkyl, C₁-C₃-haloalkyl, C₁-C₃alkoxy, C₁-C₃halo-alkoxy, halogen, cyano or by nitro, diphenylamino, or diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino, C₃-C₇-cycloalkoxy, C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, C₂-C₈dialkylamino, benzyloxy or phenoxy, wherein the benzyl and phenyl groups may in turn be substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro; R₂₇ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅alkylamino-C₁-C₅alkyl, C₂-C₈dialkyl-amino-C₁-C₅alkyl, C₃-C₇cycloalkyl-C₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyl-oxyalkyl, C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfoxyl-C₁-C₅alkyl, C₁-C₅alkyl-sulfonyl-C₁-C₅alkyl, C₂-C₈alkylideneaminooxy-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-C₁-C₅alkyl, C₁-C₅alkoxycarbonyl-C₁-C₅alkyl, C₁-C₅amino-carbonyl-C₁-C₅alkyl, C₂-C₈dialkylamino-carbonyl-C₁-C₅alkyl, C₁-C₅alkyl-carbonylamino-C₁-C₅alkyl, C₁-C₅alkylcarbonyl-(C₂-C₅alkyl)-aminoalkyl, C₃-C₆trialkylsilyl-C₁-C₅alkyl, phenyl-C₁-C₅alkyl, heteroaryl-C₁-C₅alkyl, phenoxy-C₁-C₅alkyl, heteroaryloxy-C₁-C₅alkyl, C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cyclo-alkyl, phenyl, or phenyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl or heteroarylamino, or heteroaryl or heteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diheteroarylamino, diheteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, or phenylamino, phenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, diphenylamino, diphenylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitro, C₃-C₇cyclo-alkylamino, di-C₃-C₇cycloalkylamino, C₃-C₇cycloalkoxy or C₁-C₁₀alkylcarbonyl; or an agronomically tolerable salt, isomer or enantiomer of such a compound.
 2. A compound according to claim 1, wherein Q is Q_(1.).
 3. A process for the preparation of a compound of formula I according to claim 1, wherein a compound of formula XXX Q—H  (XXX) wherein Q is Q₁, Q₂, Q₅, or Q₉, the substituents of which, with the exception of G₁, G₂, G₅, and G₉, have the meanings given above, and G₁, G₂, G₅, and G₉ are hydrogen, is reacted with a compound of formula XXXI

wherein R₁ and R₃ are as defined for formula I and Hal is chlorine, bromine or iodine, in the presence of an inert solvent, a base and a palladium catalyst at temperatures of from 30 to 250° C.
 4. A herbicidal and plant growth-inhibiting composition that comprises a herbicidally effective amount of a compound of formula I according to claim 1, on an inert carrier.
 5. A method of controlling undesired plant growth that comprises applying a herbicidally effective amount of an active ingredient of formula I according to claim 1, or of a composition comprising such an active ingredient, to the plants or to the locus thereof.
 6. A method of inhibiting plant growth that comprises applying a herbicidally effective amount of an active ingredient of formula I according to claim 1, or of a composition comprising such an active ingredient, to the plants or to the locus thereof. 